Carbon dioxide‐in‐water foams stabilized with nanoparticles and surfactant acting in synergy

Synergistic interactions at the interface of nanoparticles (bare colloidal silica) and surfactant (caprylamidopropyl betaine) led to the generation of viscous and stable CO₂‐in‐water (C/W) foams with fine texture at 19.4 MPa and 50°C. Interestingly, neither species generated C/W foams alone. The surfactant became cationic in the presence of CO₂ and adsorbed on the hydrophilic silica nanoparticle surfaces resulting in an increase in the carbon dioxide/water/nanoparticle contact angle. The surfactant also adsorbed at the CO₂–water interface, reducing interfacial tension to allow formation of finer bubbles. The foams were generated in a beadpack and characterized by apparent viscosity measurements both in the beadpack and in a capillary tube viscometer. In addition, the macroscopic foam stability was observed visually. The foam texture and viscosity were tunable by controlling the aqueous phase composition. Foam stability is discussed in terms of lamella drainage, disjoining pressure, interfacial viscosity, and hole formation. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3490–3501, 2013     

Generation of microcellular polyurethane foams via polymerization in carbon dioxide. I: Phase behavior of polyurethane precursors

On investigating the generation of microcellular polyurethane foam via reaction in carbon dioxide, we have observed that common polyurethane precursors are CO₂ miscible, whereas typically fluorinated compounds or specially designed surfactants are needed to solubilize polymers in CO₂. Both isocyanates and polyols are CO₂-miscible at workable pressures and temperatures and in useful concentrations to allow generation of polyurethane foams in CO₂. By characterizing the phase behavior of several series of propylene oxide and ethylene oxide polyols, we have observed that the combined effects of molecular weight and hydroxyl number fix the location of the phase separation pressures. In general, lower molecular weights and lower hydroxyl mole fractions produce phase boundaries at relatively lower pressures in carbon dioxide. It also has been shown that CO₂-soluble compounds may have a com̀patibilizing effect on less CO₂-soluble materials.     

泡沫薄膜液在直管内的流变学特性

针对泡沫液在多孔介质内的流动特点,对泡沫薄膜液在直管内的流变学特性进行了实验研究。按单相幂律流体假设,获得二氧化碳及氮气泡沫薄膜液的表观黏度数据。结果表明：泡沫薄膜液具有较大表观黏度并呈现剪切变稀的非牛顿流体特性。由于水溶性影响,二氧化碳泡沫液的表观黏度要小于氮气泡沫液。利用量纲分析法确定量纲1参数,对泡沫薄膜液的流变学特性进行了量纲1分析并给出基于两相流动分析的阻力模型。     

X‐ray tomography of feed‐to‐glass transition of simulated borosilicate waste glasses

High‐level waste feed composition affects the overall melting rate by influencing the chemical, thermophysical, and morphological properties of a cold cap layer that floats on the molten glass where most feed‐to‐glass reactions occur. Data from X‐ray computed tomography imaging of melting pellets comprised of a simulated high‐aluminum feed reveal the morphology of bubbles, known as the primary foam, for various feed compositions at temperatures between 600°C and 1040°C. These feeds were formulated to make glasses with viscosities ranging from 0.5 to 9.5 Pa s at 1150°C, which was accomplished by changing the SiO₂/(B₂O₃+Na₂O+Li₂O) ratio in the final glass. Pellet dimensions and profile area, average and maximum bubble areas, bubble diameter, and void fraction were evaluated. The feed viscosity strongly affects the onset of the primary foaming and the foam collapse temperature. Despite the decreasing amount of gas‐evolving components (Li₂CO₃, H₃BO₃, and Na₂CO₃), as the feed viscosity increases, the measured foam expansion rate does not decrease. This suggests that the primary foaming is not only affected by changes in the primary melt viscosity but also by the compositional reaction kinetic effects. The temperature‐dependent foam morphological data will be used to inform cold cap model development for a high‐level radioactive waste glass melter.     

Flame retardancy working mechanism of methyl‐DOPO and MPPP in flexible polyurethane foam

The chemical nature of flexible polyurethane (flex PU) foams, the low density, the high air permeability and the open cell structure cause this material to be highly flammable. The new phosphorus flame‐retardant (FR) methyl‐DOPO (9, 10‐dihydro‐9‐oxa‐methylphosphaphenanthrene‐10‐oxide) is known to show an excellent flame retarding behavior in flex PU foam by acting mainly in the gas phase. In this study, the FR working mechanism of methyl‐DOPO and its ring‐opened analogue MPPP (methylphenoxyphenyl‐phosphinate) is investigated by TGA, TG–MS, FMVSS 302 and Cone Calorimeter measurements. Under TG–MS conditions comparable concentrations of low molecular weight species such as HPO, mathrmCH₃PO or PO₂ are released. These species are able to scavenge the H‐ and OH‐radicals in the radical chain reactions of the flame leading to a significant increase in the CO/CO₂ ratio and the smoke density during cone calorimeter experiments. Finally, the flame retardancy of MPPP is determined to be less efficient in flex PU foam because of the higher vapor pressure compared with methyl‐DOPO. Here, the vaporization of methyl‐DOPO occurs in the same temperature region as the depolymerization of the urethane and the bisubstituted urea groups during pyrolysis of the foam leading to an optimal interaction. Copyright © 2010 John Wiley & Sons, Ltd.     

Dynamics and selectivity of NOx reduction in NOx storage catalytic monolith

Several nitrogen compounds can be produced during the regeneration phase in periodically operated NO_x storage and reduction catalyst (NSRC) for conversion of automobile exhaust gases. Besides the main product N₂, also NO, N₂O, and NH₃ can be formed, depending on the regeneration phase length, temperature, and gas composition. This contribution focuses on experimental evaluation of the NO_x reduction dynamics and selectivity towards the main products (NO, N₂ and NH₃) within the short rich phase, and consequent development of the corresponding global reaction-kinetic model. An industrial NSRC monolith sample of PtRh/Ba/CeO₂/ -Al₂O₃ type is employed in nearly isothermal laboratory micro-reactor. The oxygen and NO_x storage/reduction experiments are performed in the temperature range 100–500 °C in the presence of CO₂ and H₂O, using H₂, CO and C₃H₆ as the reducing agents.The spatially distributed NSRC model developed earlier is extended by the following reactions: NH₃ is formed by the reaction of H₂ with NO_x and it can further react with oxygen and NO_x deposited on the catalyst surface, producing N₂. Considering this scheme with ammonia as an active intermediate of the NO_x reduction, a good agreement with experiments is obtained in terms of the NO_x reduction dynamics and selectivity. A reduction front travelling in the flow direction along the reactor is predicted, with the NH₃ maximum on the moving boundary. When the front reaches the reactor outlet, the NH₃ peak is observed in the exhaust gas. It is assumed that the ammonia formation during the NO_x reduction by CO and HCs at higher temperatures proceed via the water gas shift and steam reforming reactions producing hydrogen. It is further demonstrated that oxygen storage effects influence the dynamics of the stored NO_x reduction. The temperature dependences of the outlet ammonia peak delay and the selectivity towards NH₃ are correlated with the effective oxygen and NO_x storage capacity.     

Pressure‐driven displacement flows of yield stress fluids: Viscosity ratio effects

We numerically investigate pressure‐driven, density‐unstable displacement flows of two miscible fluids along a near‐horizontal 2D channel. The displacing fluid is a Newtonian fluid, slightly heavier than the displaced yield stress (Bingham) fluid. The imposed displacement flow is laminar. We show that the displacement flow is mainly governed by five dimensionless numbers, and their combinations, including the Reynolds number (Re), the Bingham number (Bn), the densimetric Froude number (Fr), the viscosity ratio (m), and the channel inclination angle (β). In this work, we primarily focus on the viscosity ratio and provide a detailed understanding of the flow behaviours via studying the effects of m on displacement flow patterns, regime classifications based on slump‐type and centre‐type displacement flow regimes, leading and trailing displacement front features, and finally the effects of m at different inclination angles.     

Overpotential Behavior of Carbon Monoxide Fuel in a Molten Carbonate Fuel Cell

The overpotential of carbon monoxide (CO) fuel was analyzed with a 100‐cm² class molten carbonate fuel cell. The overpotential at the anode was measured using the steady state polarization, inert gas step addition, and reactant gas addition methods. Then, the overpotential was compared between normal hydrogen fuel (H₂:CO₂:H₂O = 0.69:0.17:0.14 atm, inlet composition) and CO fuels (CO:CO₂:H₂O = 0.5:0.5:0 atm and 0.43:0.43:0.14 atm, inlet compositions). The CO fuel without H₂O showed a much greater overpotential at 150 mA cm^–2 than the CO fuel with H₂O. This implies that the water‐gas‐shift reaction prevails at the anode and humidification of CO fuel is an efficient way to reduce anodic overpotential. The anodic overpotential with CO:CO₂:H₂O = 0.43:0.43:0.14 atm was about 73% of that of the H₂ fuel at 150 mA cm^–2. The anode showed gas‐phase mass‐transfer limitations with CO fuels.     

Aqueous‐phase ketonization of acetic acid over Zr/Mn mixed oxides

Aqueous‐phase ketonization possesses significant advantages over gas‐ or organic‐phase ketonization for improved conversion efficiency of aqueous fraction accompanied by algal bio‐oil production. In this study, synthetized ZrO₂ and Zr/Mn oxides are used for aqueous‐phase ketonization of acetic acid. ZrMn_0.5O_x shows the highest ketonization activity at 340°C for 12 h, achieving maximum acetone yield of 88.27%; and all catalysts exhibited selectivity higher than 96.75%. Apparent activation energy and acid reaction order are 161.2 kJ mol^?1 and 0.70, respectively. Results suggest high ketonization activity of poorly crystallized tetragonal ZrO₂. Addition of Mn results in ZrO₂/MnO_x solid solution and improves active sites. Acid property and Mn⁴⁺ content are important factors, and oxygen vacancy demonstrates relationship with ketonization activity for ZrO₂. Examination of recovered catalysts indicates that ZrMn_yO_x exhibits improved stability, and Mn leaching and crystal phase transformation are main causes of deactivation in aqueous‐phase ketonization. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2958–2967, 2017     

Domain Structure Evolutions During the Poling Process for [011]‐Oriented PMN–xPT Crystals Across the MPB Region

The poling effect on the [011]‐oriented (1?x)Pb(Mg_1/3Nb_2/3)O₃‐xPbTiO₃ (PMN–xPT) single crystals across the morphotropic phase boundary (MPB) was studied. The dielectric and piezoelectric properties were investigated as a function of the poling field. Domain structure evolutions during the poling process were recorded. In the unpoled PMN–xPT phase diagram, an apparent rhombohedral (R)‐tetragonal (T) phase boundary exists. With room‐temperature poling, the structure transformation sequence strongly depends on the composition. The crystal experiences a direct transition to the 2R/2T domain state in the rhombohedral or tetragonal phase field beyond the MPB region, whereas within the MPB zone it is hard to achieve the 2R/2T engineered configuration although the initial state is either rhombohedral or tetragonal as well. The piezoelectric responses of the MPB·PMN–xPTs are extraordinary weak (d₃₃ ~ 250 pC/N), in contrast to the [011]‐oriented multidomain PMN–xPTs with ultrahigh‐piezoelectric coefficient (d₃₃ > 1000 pC/N). We demonstrate that a slight composition variation near the MPB will significantly influence the domain evolution route and piezoelectricity for the [011]‐oriented PMN–xPT crystals. We also confirm the feasibility to realize the 2R/2T engineered domain configuration for the [011]‐oriented MPB crystals, which will extend the desired portion of the Bridgeman‐grown boules with optimal piezoelectric properties.     

The pyrolysis behaviors of polyimide foam derived from 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride/4,4′‐oxydianiline

The thermal stability and pyrolysis behaviors of polyimide (PI) foam derived from 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA)/4,4′‐oxydianiline (4,4′‐ODA) in air and in nitrogen were studied. The decomposition products of PI foam were analyzed by thermogravimetry‐Fourier transform infrared spectroscopy (TG‐FTIR). Several integral and differential methods reported in the literatures were used in decomposition kinetics analysis of PI foam. The results indicated that the PI foam was easier to decompose in air than in nitrogen, with ～ 55% residue remaining in nitrogen versus zero in air at 800^oC. The main pyrolysis products were CO₂, CO, and H₂O in air and CO₂, CO, H₂O, and small organic molecules in nitrogen. The different dynamic methods gave similar results that the apparent activation energies, pre‐exponential factors, and reaction orders were higher in nitrogen than those in air. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Reaction Pathways for Ammonia Formation on Lean NOx Trap/Reduction System: A Spectroscopic Infrared Investigation

This study is devoted to an operando study of Pt–Rh/Al₂O₃–BaO lean-NO_x trap catalyst during the regeneration with H₂/CO reaction mixture. Particular attention was paid to the influence of CO coexisting with H₂ during the regeneration that can simulate the regeneration step by using reformate composed of CO and H₂. In rich H₂ mixture ammonia predominantly forms. As expected, strongly chemisorbed CO molecules over noble metals lower the efficiency of the trap at 150 °C. Successive hydrogenation of N atoms to ammonia predominates in our conditions. However, the comparison of the outlet gas composition with infrared spectral features also suggests a minor participation of isocyanate species (NCO) as possible intermediates in the production of ammonia especially for long regeneration duration in the absence of water. Interestingly, ammonia formation as reducing agent for the selective reduction of NO can stimulate practical applications for further coupling lean-NO_x trap with SCR catalysts.     

Preparation and morphology characterization of microcellular styrene‐co‐acrylonitrile (SAN) foam processed in supercritical CO2

Microcellular polymeric foam structures have been generated using a pressure‐induced phase separation in concentrated mixtures of supercritical CO₂ and styrene‐co‐acrylonitrile (SAN). The process typically generates a microcellular core structure encased by a non‐porous skin. Pore growth occurs through two mechanisms: diffusion of CO₂ from polymer‐rich regions into the pores and also through CO₂ gas expansion. The effects of saturation pressure, temperature and swelling time on the cell size, cell density and bulk density of the porous materials have been studied. Higher CO₂ pressures (hence, higher fluid density) provided more CO₂ molecules for foaming, generated lower interfacial tension and viscosity in the polymer matrix, and thus produced lower cell size but higher cell densities. This trend was similar to what was observed in swelling time series. While the average cell size increased with increasing temperature, the cell density decreased. The trend of bulk density was similar to that of cell size. © 2000 Society of Chemical Industry     

Stability improvement of CO2 foam for enhanced oil‐recovery applications using polyelectrolytes and polyelectrolyte complex nanoparticles

CO₂ foam for enhanced oil‐recovery applications has been traditionally used in order to address mobility‐control problems that occur during CO₂ flooding. However, the supercritical CO₂ foam generated by surfactant has a few shortcomings, such as loss of surfactant to the formation due to adsorption and lack of a stable front in the presence of crude oil. These problems arise because surfactants dynamically leave and enter the foam interface. We discuss the addition of polyelectrolytes and polyelectrolyte complex nanoparticles (PECNP) to the surfactant solution to stabilize the interface using electrostatic forces to generate stronger and longer‐lasting foams. An optimized ratio and pH of the polyelectrolytes was used to generate the nanoparticles. Thereafter we studied the interaction of the polyelectrolyte–surfactant CO₂ foam and the polyelectrolyte complex nanoparticle–surfactant CO₂ foam with crude oil in a high‐pressure, high‐temperature static view cell. The nanoparticle–surfactant CO₂ foam system was found to be more durable in the presence of crude oil. Understanding the rheology of the foam becomes crucial in determining the effect of shear on the viscosity of the foam. A high‐pressure, high‐temperature rheometer setup was used to shear the CO₂ foam for the three different systems, and the viscosity was measured with time. It was found that the viscosity of the CO₂ foams generated by these new systems of polyelectrolytes was slightly better than the surfactant‐generated CO₂ foams. Core‐flood experiments were conducted in the absence and presence of crude oil to understand the foam mobility and the oil recovered. The core‐flood experiments in the presence of crude oil show promising results for the CO₂ foams generated by nanoparticle–surfactant and polyelectrolyte–surfactant systems. This paper also reviews the extent of damage, if any, that could be caused by the injection of nanoparticles. It was observed that the PECNP–surfactant system produced 58.33% of the residual oil, while the surfactant system itself produced 47.6% of the residual oil in place. Most importantly, the PECNP system produced 9.1% of the oil left after the core was flooded with the surfactant foam system. This proves that the PECNP system was able to extract more oil from the core when the surfactant foam system was already injected. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44491.     

Blends containing amphiphilic polymers. V. Compatibilization of N‐alkylitaconamic acid‐co‐styrene copolymers with interacting polymers

The phase behavior of blends containing N‐alkylitaconamic acid‐co‐styrene copolymers (NAIA‐co‐S) with poly(N‐vinyl‐2‐pyrrolidone) (PVP) of two different weight average molecular weights (M _w ), poly(2‐vinylpyridine) (P2VPy) and poly(4‐vinylpyridine) (P4VPy), was analyzed by differential scanning calorimetry and Fourier transform infrared spectroscopy. Copolymers containing 80% S are miscible with PVP₁₀, PVP₂₄, and P4VPy over the whole range of composition. In the case of blends with P2VPy, miscibility is observed only for the first three members of the series, i.e., NEIA‐co‐S, NPIA‐co‐S, and NBIA‐co‐S. For copolymers containing hexyl to dodecyl moieties, phase separation is observed in blends with P2VPy. Copolymers containing 50% S are miscible over the whole range of composition irrespective of the homopolymer and the length of the side chain of the itaconamic moiety of the copolymer. This behavior is interpreted in terms of steric hindrance, in the sense that the copolymers with long side chains are not able to interact with the nitrogen of P2VPy because of the position in the aromatic ring. The interactions between copolymers and homopolymers are discussed in terms of specific interactions like hydrogen bonds between the itaconamic moiety and the different functional groups of the homopolymers, together with the hydrophobic interaction, which cannot be disregarded. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2512–2519, 2006     

Structure,electrical, and thermal expansion properties of PZnTe–PZT ternary system piezoelectric ceramics

xPb(Zn_0.5Te_0.5)O₃–(1?x)Pb(Zr_0.5Ti_0.5)O₃ (PZnTe–PZT) ceramics were prepared by the solid‐state reaction method. The phase structure, microstructure, ferroelectric and dielectric properties and thermal expansion properties were systematically investigated. X‐ray diffraction analysis showed the morphotropic phase boundary (MPB) existed at the composition of x = 0.08, which was the coexistence of the rhombohedral phase and the tetragonal phase. The grain size of ceramics decreased rapidly from 10‐20 μm to 1‐3 μm when the PZnTe was added in. The PZnTe–PZT ceramics at the MPB composition showed the largest high field effective piezoelectric coefficient and the lowest strain hysteresis H. The dielectric permittivity and phase transition temperature exhibited strongly compositional dependence. A good linear relation was shown in T_m temperature vs x content and a DPT behavior was found in xPZnTe–(1?x)PZT (x = 0.02‐0.08). The thermal expansion properties showed a low thermal expansion coefficient in the low temperature while a high thermal expansion coefficient in the high temperature. Besides, the thermal expansion curve also showed the characteristic of DPT in PZnTe–PZT ceramics.     

Physical mixtures as simple and efficient alternative to alloy carriers in chemical looping processes

Chemical looping combustion is a clean combustion technology for fossil or renewable fuels. In a previous demonstration, chemical looping was applied to CO₂ activation via reduction to CO with concurrent production of synthesis gas (CO + H₂) from CH₄ via rationally designed Fe‐Ni alloys. Here, it is demonstrated that that a simple physical mixture can even outperform the equivalent alloy based on an intricate gas phase mediated coupling between the two metals: Ni cracks methane to carbon and H₂. The latter then reduces iron oxide carrier, forming steam, which gasifies the carbon deposits on Ni to produce a mixture of CO + H₂, thus regenerating the active Ni surface. It was suggested that the principle demonstrated here—the gas phase‐mediated coupling of two solid reactants with distinct functionalities—should be applicable broadly toward oxidation reactions and hence opens a new avenue for rational design of chemical looping processes. © 2016 American Institute of Chemical Engineers AIChE J, 63: 51–59, 2017     

Cyclic Lean Reduction of NO by CO in Excess H2O on Pt–Rh/Ba/Al2O3: Elucidating Mechanistic Features and Catalyst Performance

This study provides insight into the mechanistic and performance features of the cyclic reduction of NO_x by CO in the presence and absence of excess water on a Pt–Rh/Ba/Al₂O₃ NO_x storage and reduction catalyst. At low temperatures (150–200 °C), CO is ineffective in reducing NO_x due to self-inhibition while at temperatures exceeding 200 °C, CO effectively reduces NO_x to main product N₂ (selectivity >70 %) and byproduct N₂O. The addition of H₂O at these temperatures has a significant promoting effect on NO_x conversion while leading to a slight drop in the CO conversion, indicating a more efficient and selective lean reduction process. The appearance of NH₃ as a product is attributed either to isocyanate (NCO) hydrolysis and/or reduction of NO_x by H₂ formed by the water gas shift chemistry. After the switch from the rich to lean phase, second maxima are observed in the N₂O and CO₂ concentrations versus time, in addition to the maxima observed during the rich phase. These and other product evolution trends provide evidence for the involvement of NCOs as important intermediates, formed during the CO reduction of NO on the precious metal components, followed by their spillover to the storage component. The reversible storage of the NCOs on the Al₂O₃ and BaO and their reactivity appears to be an important pathway during cyclic operation on Pt–Rh/Ba/Al₂O₃ catalyst. In the absence of water the NCOs are not completely reacted away during the rich phase, which leads to their reaction with NO and O₂ upon switching to the subsequent lean phase, as evidenced by the evolution of N₂, N₂O and CO₂. In contrast, negligible product evolution is observed during the lean phase in the presence of water. This is consistent with a rapid hydrolysis of NCOs to NH₃, which results in a deeper regeneration of the catalyst due in part to the reaction of the NH₃ with stored NO_x. The data reveal more efficient utilization of CO for reducing NO_x in the presence of water which further underscores the NCO mechanism. Phenomenological pathways based on the data are proposed that describes the cyclic reduction of NO_x by CO under dry and wet conditions.     

Correlation of the melt rheological properties with the foaming behavior of immiscible blends of poly(2,6‐dimethyl‐1,4‐phenylene ether) and poly(styrene‐co‐acrylonitrile)

Immiscible blends of poly(2,6‐dimethyl‐1,4‐phenylene ether)/poly(styrene‐co‐acrylonitrile) (PPE/SAN) were batch‐foamed using CO₂ as a blowing agent as a function of foaming temperature, foaming time, and blend composition. Evaluation of the resulting cellular morphology revealed an enhanced foamability of SAN with PPE contents up to 20 wt% as indicated by a similar volume expansion but a significantly reduced mean cell size. This behavior is related to a heterogeneous nucleation activity by the dispersed PPE phase. A further increasing PPE content, however, leads to increasing foam densities as well as nonuniform foam morphologies. The changes in the foaming behavior can be correlated with the melt rheological properties and the corresponding blend morphology. Shear‐rheological investigations revealed an onset of percolation of the dispersed PPE phase between 20 and 40 wt%, and a transition towards cocontinuity at 60 wt%. The materials response under uniaxial elongational flow, as assessed by Rheotens measurements, revealed an increase in elongational viscosity scaling with the PPE content, similar to the shear data. However, the strain hardening behavior was reduced by increasing PPE contents and, at 20 wt%, the drawability revealed a significant drop‐both phenomena limiting the foamability of polymers. In summary, the present study discusses fundamental aspects of foaming immiscible PPE/SAN blends. POLYM. ENG. SCI., 48:2111–2125, 2008. © 2008 Society of Plastics Engineers     

Novel magnetoelectric composites of cobalt iron alloy and barium titanate

Magnetoelectric barium titanate ceramics with embedded cobalt iron alloy particles (Co_1/3Fe_2/3)_x–(BaTiO₃)_(1?x), with x=0.2, 0.4, and 0.6, were prepared by a polyol‐mediated synthesis with subsequent sintering in a reducing forming gas atmosphere. The samples were characterized by XRD and SEM/EDX measurements. The sizes of the Co_1/3Fe_2/3 grains increase with x. Impedance spectroscopy showed a behavior similar to pure BaTiO₃, in particular the occurrence of the ferroelectric‐paraelectric phase transition, and high permittivities for the sample with x=0.6, that is, near the percolation threshold. The samples exhibit soft ferromagnetic properties with large saturation magnetizations of 2.5 μ_B/atom and narrow hystereses. Detailed magnetoelectric investigations revealed a unique DC‐field dependence of α_ME for all three compositions. Most remarkably, the sample with x=0.4 possesses a broad ME hysteresis and an inversion of the sign of α_ME at 5 kOe.