Phase transition and negative thermal expansion properties of Sc2−xCrxMo3O12

The crystal structure, phase transition and thermal expansion behaviors of solid solutions Sc_2−xCr_xMo₃O₁₂ (0≤x≤2) were investigated using X-ray diffraction (XRD) and differential scanning calorimetry (DSC). At room temperature, samples with x≤0.7 and x≥0.8 crystallize in orthorhombic and monoclinic structures, respectively. DSC result indicates that the phase transition of Sc_0.5Cr_1.5Mo₃O₁₂ from monoclinic to orthorhombic structure occurs at 203.66 °C. The linear thermal expansion coefficient of orthorhombic phases varies from −2.334×10⁻⁶ °C⁻¹ to 0.993×10⁻⁶ °C⁻¹ when x increases from 0.0 to 1.5. The near-zero linear thermal expansion coefficients of −0.512×10⁻⁶ °C⁻¹ and −0.466×10⁻⁶ °C⁻¹ are observed for compounds with x=0.5 and 0.7, respectively.     

Electrochemical properties of La1−xSrxFeO3 (x = 0.2, 0.4) as negative electrode of Ni-MH batteries

La_(1−x)Sr_xFeO₃ (x = 0.2,0.4) powders were prepared by a stearic acid combustion method, and their phase structure and electrochemical properties were investigated systematically. X-ray diffraction (XRD) analysis shows that La_(1−x)Sr_xFeO₃ perovskite-type oxides consist of single-phase orthorhombic structure (x = 0.2) and rhombohedral one (x = 0.4), respectively. The electrochemical test shows that the reaction at La_(1−x)Sr_xFeO₃ oxide electrodes are reversible. The discharge capacities of La_(1−x)Sr_xFeO₃ oxide electrodes increase as the temperature rises. With the increase of the temperature from 298 K to 333 K, their initial discharge capacity mounts up from 324.4 mA h g⁻¹ to 543.0 mA h g⁻¹ (when x = 0.2) and from 147.0 mA h g⁻¹ to 501.5 mA h g⁻¹ (when x = 0.4) at the current density of 31.25 mA g⁻¹, respectively. After 20 charge-discharge cycles, they still remain perovskite-type structure. Being similar to the relationship between the discharge capacity and the temperature, the electrochemical kinetic analysis indicates that the exchange current density and proton diffusion coefficient of La_(1−x)Sr_xFeO₃ oxide electrodes increase with the increase of the temperature. Compared with La_0.8Sr_0.2FeO₃, La_0.6Sr_0.4FeO₃ electrode is a more promising candidate for electrochemical hydrogen storage because of its higher cycle capacity at various temperatures.     

Preparation and microstructural characterization of (Nd1−xGdx)2(Ce1−xZrx)2O7 solid solutions

(Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ (0 ≤ x ≤ 1.0) powders with an average particle size of 100 nm were synthesized with chemical-coprecipitation and calcination method, and were characterized by X-ray diffractometry and scanning electron microscopy. The sintering behaviour of (Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ powders was studied by pressureless sintering at 1600–1700 °C for 10 h in air. The relative densities of (Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ solid solutions increase with increasing the sintering temperature, and gradually decrease with increasing the content of neodymium and cerium at identical temperature levels. (Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ solid solutions have a single phase of defect fluorite-type structure among all the composition combinations studied. The lattice parameters of (Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ solid solutions agree well with the Vegard's rule.     

Kinetics and PEMFC performance of RuxMoySez nanoparticles as a cathode catalyst

Kinetics of Ru_xMo_ySe_z nanoparticles dispersed on carbon powder was studied in 0.5 M H₂SO₄ electrolyte towards the oxygen reduction reaction (ORR) and as cathode catalysts for a proton exchange membrane fuel cell (PEMFC). Ru_xMo_ySe_z catalyst was synthesized by decarbonylation of transition-metal carbonyl compounds for 3 h in organic solvent. The powder was characterized by X-ray diffraction (XRD), and transmission electron microscopy (TEM) techniques. Catalyst is composed of uniform agglomerates of nanocrystalline particles with an estimated composition of Ru₆Mo₁Se₃, embedded in an amorphous phase. The electrochemical activity was studied by rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques. Tafel slopes for the ORR remain invariant with temperature at −0.116 V dec⁻¹ with an increase of the charge transfer coefficient in dα/dT = 1.6 × 10⁻³, attributed to an entropy turnover contribution to the electrocatalytic reaction. The effect of temperature on the ORR kinetics was analyzed resulting in an apparent activation energy of 45.6 ± 0.5 kJ mol⁻¹. The catalyst generates less than 2.5% hydrogen peroxide during oxygen reduction. The Ru_xMo_ySe_z nanoparticles dispersed on a carbon powder were tested as cathode electrocatalyst in a single fuel cell. The membrane-electrode assembly (MEA), included Nafion^® 112 as polymer electrolyte membrane and commercial carbon supported Pt (10 wt%Pt/C-Etek) as anode catalyst. It was found that the maximum performance achieved for the electro-reduction of oxygen was with a loading of 1.0 mg cm⁻² Ru_xMo_ySe_z 20 wt%/C, arriving to a power density of 240 mW cm⁻² at 0.3 V and 80 °C.     

Electrical conductivity and redox stability of La2Mo2−xWxO9 materials

A series of compounds La₂Mo_2−xW_xO₉ (x = 0-2) were synthesized using a freeze-dried precursor method at relatively low temperatures (673-823 K). These materials were characterised by thermogravimetric and differential thermal analysis (TG/DTA), differential scanning calorimetric (DSC), X-ray diffraction (XRD), and transmission electron microscopy (TEM) and dilatometric measurements. Oxygen stoichiometry was evaluated by coulometric titration and thermogravimetric analysis at 873-1273 K. The ionic and electronic conductivities of these materials were analysed by impedance spectroscopy and a Hebb-Wagner ion-blocking method under moderately reducing conditions. The presence of W⁶⁺ leads to an increase of the stability range (about 10⁻¹⁶ Pa for La₂Mo_0.5W_1.5O₉ at 1073 K) and prevents oxygen loss and amorphisation. Within the stability range, the electronic conductivity increases gradually as the temperature increases and as the oxygen partial pressure reduces. This indicates that the electronic transport is mainly n-type as a result of the oxygen-content decreasing in the molybdate lattice. Further reduction of the oxygen partial pressure gave rise to the decomposition of La₂Mo_2−xW_xO₉, leading to the formation of new phases with molybdenum in lower oxidation states, which further enhances the electronic conductivity. The results of the coulometric titration and the thermogravimetric studies under a dry 5% H₂/Ar flow suggest that tungsten doped lanthanum molybdate materials can be used as electrolyte only at low temperature and under moderate reducing conditions.     

Synthesis and negative thermal expansion property of Y2−xLaxW3O12 (0≤x≤2)

Y_2−xLa_xW₃O₁₂ solid solutions were successfully synthesized by the solid state reaction method. The microstructure, hygroscopicity and thermal expansion property of the resulting samples were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FESEM) and thermal mechanical analysis (TMA). Results indicate that the structural phase transition of the Y_2−xLa_xW₃O₁₂ changes from orthorhombic to monoclinic with increasing substituted content of lanthanum. The pure phase can form for 0≤x≤0.4 with orthorhombic structure and for 1.5≤x≤2 with monoclinic one. High lanthanum content leads to a low relative density of Y_2−xLa_xW₃O₁₂ ceramic. Thermal expansion coefficients of the Y_2−xLa_xW₃O₁₂ (0≤x≤2) ceramics also vary from −9.59×10⁻⁶ K⁻¹ to 2.06×10⁻⁶ K⁻¹ with increasing substituted content of lanthanum. The obtained Y_0.25La_1.75W₃O₁₂ ceramic shows almost zero thermal expansion and its average linear thermal expansion coefficient is −0.66×10⁻⁶ K⁻¹ from 103 °C to 700 °C.     

Sintering behavior and microwave dielectric properties of a new low-permittivity ceramic system Ca(Mg1−xAlx)(Si1−x/2Alx/2)2O6

The diopside ceramics with a formula of Ca(Mg_1−xAl_x)(Si_1−x/2Al_x/2)₂O₆ (x=0.01–0.3) were synthesized via a traditional solid-state reaction method, and their solid solubility, sintering behavior and microwave dielectric properties were investigated. The results revealed that the solubility limit of Al₂O₃ in Ca(Mg_1−xAl_x)(Si_1−x/2Al_x/2)₂O₆, which is defined as x, was between 0.15 and 0.2, and a second phase of CaAl₂SiO₆ presented when the x value reached 0.2. Appropriate Al³⁺ substitution for Mg²⁺ and Si⁴⁺ could promote the sintering process and lower the densification temperature, and a broadened densification temperature range of 1250–1300 °C was obtained for the compositions of x=0.08–0.15. With the increase of the x value, the dielectric constant (ε_r) increased roughly linearly, and the temperature coefficient of frequency (τ_f) showed a rising trend. The Q×f values increased from 57,322 GHz to 59,772 GHz as the x value increased from 0.01 to 0.08, and then they were saturated in the range of x=0.08–0.2. Further increase of the x value (x≥0.25) deteriorated the microwave dielectric properties. Good microwave dielectric properties of ε_r=7.89, Q×f=59,772 GHz and τ_f=−42.12 ppm/°C were obtained for the ceramics with the composition of x=0.08 sintered at 1275 °C.     

Structure,magnetic and electrical transport properties of the perovskites Sm1−xCaxFe1−xMnxO3

The structure of series Sm_1−xCa_xFe_1−xMn_xO₃ (0.0 ≤ x ≤ 1.0) compounds was investigated. The lattice parameters increase with coupled substitution Sm³⁺ by Ca²⁺ and Mn⁴⁺ for Fe³⁺. The variation of parameter, c, is larger than that of a and b, respectivly. The detailed analysis of magnetic properties of series Sm_1−xCa_xFe_1−xMn_xO₃ (0.1 ≤ x ≤ 0.9) shows that local magnetic interaction between Fe³⁺ and Fe³⁺ and Mn⁴⁺ and Mn⁴⁺ at below magnetic transition temperature is antiferromagnetic. Above magnetic transition temperature the presence of large magnetic cluster is proposed and the sizes of magnetic clusters decrease with Mn⁴⁺. The electrical transport behaviors related with small polaron hopping and variable range hopping models.     

Synthesis and properties of (BaxPb1−x)(Zn1/3Nb2/3)O3 relaxor ferroelectric ceramics using a reaction-sintering process

(Ba_xPb_1−x)(Zn_1/3Nb_2/3)O₃ (BPZN; x = 0.06–0.1) relaxor ferroelectric ceramics produced using a reaction-sintering process were investigated. Without any calcination involved, the mixture of raw materials was pressed and sintered directly. BPZN ceramics of 100% perovskite phase were obtained. Highly dense BPZN ceramics with a density higher than 98.5% of theoretical density could be obtained. Maximum dielectric constant K_max 13,500 (at 75 °C), 19,600 (at 50 °C) and 14,800 (at 28 °C) at 1 kHz could be obtained in 6BPZN, 8BPZN and 10BPZN, respectively. Dielectric maximum temperature (T_max) in BPZN ceramics via reaction-sintering process is lower than BPZN ceramics prepared via B-site precursor route.     

Preparation of morphology controlled Th1 − xUxO2 sintered pellets from low-temperature precursors

Dense sintered samples of Th_1 − xU_xO₂ solid solutions were prepared from the initial precipitation of oxalate precursors through two different wet chemical routes, based either on the direct precipitation of the cations or on the use of hydrothermal method. For both low-temperature precursors, the specific surface area was followed versus the heating temperature and the influence of the conversion step on the oxide powder reactivity was evidenced since it allowed to obtain reactive surfaces in the range of 15-45 m² g⁻¹ without any additional grinding step. From dilatometric studies, the operating conditions required for the complete densification of the Th_1 − xU_xO₂ pellets were set to a heat treatment of 3 h at 1500 °C. In these conditions, the density of the samples lies between 94% and 99% of the calculated value whatever the preparation method chosen which appeared very promising compared to the results already reported under inert atmosphere. The initial precipitation of low-temperature precursors thus allowed to lower the sintering temperature by about 100 °C while the use of hydrothermal conditions significantly improved the cationic distribution in the sintered samples, as shown from EPMA statistical experiments.     

Polypyrrole and La1−xSrxMnO3 (0≤ x ≤0.4) composite electrodes for electroreduction of oxygen in alkaline medium

Composite G/PPy/PPy(La_1−xSr_xMnO₃)/PPy electrodes made of the perovskite La_1−xSr_xMnO₃ embedded into a polypyrrole (PPy) layer, sandwiched between two pure PPy films, electrodeposited on a graphite support were investigated for electrocatalysis of the oxygen reduction reaction (ORR). PPy and PPy(La_1−xSr_xMnO₃) (0≤ x ≤0.4) successive layers have been obtained on polished and pretreated graphite electrodes following sequential electrodeposition technique. The electrolytes used in the electrodeposition process were Ar saturated 0.1 mol dm⁻³ pyrrole (Py) plus 0.05 mol dm⁻³ K₂SO₄ with and without containing a suspension of 8.33 g L⁻¹ oxide powder. Films were characterized by XRD, SEM, linear sweep voltammetry, cyclic voltammetry (CV) and electrochemical impedance (EI) spectroscopy. Electrochemical investigations were carried out at pH 12 in a 0.5 mol dm⁻³ K₂SO₄ plus 5 mmol dm⁻³ KOH, under both oxygenated and deoxygenated conditions. Results indicate that the porosity of the PPy matrix is considerably enhanced in presence of oxide particles. Sr substitution is found to have little influence on the electrocatalytic activity of the composite electrode towards the ORR. However, the rate of oxygen reduction decreases with decreasing pH of the electrolyte from pH 12 to pH 6. It is noteworthy that in contrast to a non-composite electrode of the same oxide in film form, the composite electrode exhibits much better electrocatalytic activity for the ORR.     

Double channel electrode flow cell application to the study of HO2 production on MnxCo3−xO4 (0 ≤ x ≤ 1) spinel films

We conducted a study on the electroreduction of O₂ in alkaline solution at room temperature on pure thin oxide electrodes of composition Mn_xCo_3−xO₄ (0 ≤ x ≤ 1) using the double channel electrode flow cell (DCEFC). The oxides were prepared at 150 °C and deposited by spray pyrolysis onto titanium substrates. The oxygen reduction reaction (orr) occurs through “interactive” and “parallel” pathways, and the ratio of O₂ molecules reduced to OH⁻ ions with respect to those reduced to HO₂⁻ ions depends on the oxide stoichiometry and on the applied overpotential. The formation of HO₂⁻ increases when the manganese concentration increases. The results obtained for the orr show that the number of electrons transferred per O₂ molecule decreases from 3 to 2 and the ratio k₁/k₂ (the rate constants for direct reduction to OH⁻ and indirect reduction to HO₂⁻) increases, respectively, in the overpotential studied range (−0.05 to −0.6 V). The Mn³⁺ ions placed in the B-sites of the spinel structure seem to be the active centres, where hydrogen peroxide is formed.     

Improved cycling performance of oxygen-stoichiometric spinel Li1+xAlyMn2−x−yO4+δ at elevated temperature

Li_1+xAl_yMn_2−x−yO_4±δ spinel cathode materials for lithium-ion batteries have been prepared by two methods, a specific two-step and the conventional one-step solid-state calcination methods. Compared with the conventional method, the new two-step method can guarantee the oxygen stoichiometry in spinel samples as well as reduced surface area. These characters lead to the improvement in cycling performance of spinel cathode even at elevated temperature. Moreover, the increase in doping amount of Al into Mn-spinel contributes to smearing the oxygen deficiency at high calcination temperature (1000 °C). The oxygen stoichiometric spinel samples exhibited greatly improved cycling performance. Further, Mn dissolution from spinel cathodes into the electrolyte was sufficiently suppressed even at elevated temperature of 60 °C. This beneficial influence would be reflected more remarkably in the cycles of lithium-ion full cells (spinel/C).     

Synthesis and tunable thermal expansion properties of Sc2−xYxW3O12 solid solutions

A new series of rare earth solid solutions Sc_2−xY_xW₃O₁₂ was successfully synthesized by the conventional solid-state method. Effects of doping ion yttrium on the crystal structure, morphology and thermal expansion property of as-prepared Sc_2−xY_xW₃O₁₂ ceramics were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TG), field emission scanning electron microscope (FE-SEM) and thermal mechanical analyzer (TMA). Results indicate that the obtained Sc_2−xY_xW₃O₁₂ samples with Y doping of 0≤x≤0.5 are in the form of orthorhombic Sc₂W₃O₁₂-structure and show negative thermal expansion (NTE) from room temperature to 600 °C; while as-synthesized materials with Y doping of 1.5≤x≤2 take hygroscopic Y₂W₃O₁₂·nH₂O-structure at room temperature and exhibit NTE only after losing water molecules. It is suggested that the obvious difference in crystal structure leads to different thermal expansion behaviors in Sc_2−xY_xW₃O₁₂. Thus it is proposed that thermal expansion properties of Sc_2−xY_xW₃O₁₂ can be adjusted by the employment of Y dopant; the obtained Sc_1.5Y_0.5W₃O₁₂ ceramic shows almost zero thermal expansion and its average linear thermal expansion coefficient is −0.00683×10⁻⁶ °C⁻¹ in the 25–250 °C range.     

Characterization of Mg1−xNixAl2O4 solid solutions prepared by combustion synthesis

Mg_1−xNi_xAl₂O₄ (x = 0, 0.25, 0.5, 0.75 and 1) solid solutions have been prepared by combustion synthesis. After annealing the combustion synthesized powders at 1000 °C for 3 h single-phase Mg_1−xNi_xAl₂O₄ was obtained over the entire range of compositions. The lattice parameter of Mg_1−xNi_xAl₂O₄ gradually increased from 8.049 Å (NiAl₂O₄) to 8.085 Å (MgAl₂O₄), which certified the formation of the spinel solid solutions. All samples prepared by combustion synthesis had blue color shades, denoting the inclusion of Ni²⁺ in the spinel structure in octahedral and tetrahedral configuration. The crystallite size of Mg_1−xNi_xAl₂O₄ was in the range of 35-39 nm and the specific surface area varied between 5.8 and 7.0 m²/g.     

Microwave dielectric properties of Ba3Ti4−x(Zn1/3Nb2/3)xNb4O21 for low temperature co-fired ceramics

The effects of substitution of (Zn_1/3Nb_2/3) for Ti on the sintering behavior and microwave dielectric properties of Ba₃Ti_4−x(Zn_1/3Nb_2/3)_xNb₄O₂₁ (0 ≤ x ≤ 4) ceramics have been investigated. The dielectric constant (?_r) and the temperature coefficient of the resonant frequency (τ_f) of Ba₃Ti_4−x(Zn_1/3Nb_2/3)_xNb₄O₂₁ ceramics decreased with increasing x. However, the Q × f values enhanced with the substitution of (Zn_1/3Nb_2/3) for Ti. It was found that a small amount of MnCO₃-CuO (MC) and ZnO-B₂O₃-SiO₂ (ZBS) glass additives to Ba₃Ti_4−x(Zn_1/3Nb_2/3)_xNb₄O₂₁ (x = 2) ceramics lowered the sintering temperature from 1250 to 900 °C. And Ba₃Ti_4−x(Zn_1/3Nb_2/3)_xNb₄O₂₁ (x = 2) ceramics with 1 wt% MC and 1 wt% ZBS sintered at 900 °C for 2 h showed excellent dielectric properties: ?_r = 53, Q × f = 14,600 GHz, τ_f = 6 ppm/°C. Moreover, it has a chemical compatibility with silver, which made it as a promising material for low temperature co-fired ceramics technology application.     

Study on the rapid synthesis of LiNi1−xCoxO2 cathode material for lithium secondary battery

LiNi_1−xCo_xO₂ (x = 0, 0.1, 0.2) cathode materials were successfully synthesized by a rheological phase reaction method with calcination time of 0.5 h at 800 °C. All obtained powders are pure phase with α-NaFeO₂ structure (R-3m space group). The samples deliver an initial discharge capacity of 182, 199 and 189 mAh g⁻¹ (25 mA g⁻¹, 4.35-3.0 V), respectively. The reaction mechanism was also discussed, which consists of a series of defect reactions. As a result of these defect reactions, the reaction of forming LiNi_1−xCo_xO₂ takes place in high speed.     

FexCo0.5−xNi0.5-SDC anodes for low-temperature solid oxide fuel cells

Trimetal alloys, Fe_xCo_0.5−xNi_0.5 (x = 0.1, 0.2, 0.25, 0.3, 0.4), were studied as anodes for low-temperature solid oxide fuel cells (LT-SOFCs) based on GDC (Ce_0.9Gd_0.1O_1.95) electrolytes. The alloys were formed by in situ reduction of Fe_xCo_0.5−xNi_0.5O_y composites, which were synthesized using a glycine-nitrate technique. Symmetrical cells consisted of Fe_xCo_0.5−xNi_0.5-SDC electrodes and GDC electrolytes, and single cells consisted of Fe_xCo_0.5−xNi_0.5-SDC (Ce_0.8Sm_0.2O_1.9) anodes, GDC electrolytes, and SSC (Sm_0.5Sr_0.5CoO₃)-SDC cathodes were prepared using a co-pressing and co-firing process. Interfacial polarization resistances and I-V curves of these cells were measured at temperature from 450 to 600 °C. With Fe_0.25Co_0.25Ni_0.5-SDC as anodes, the cells showed the lowest interfacial resistance and highest power density. For example, at 600 °C, the resistance was about 0.11 Ω cm² and power density was about 750 mW cm⁻² when humidified (3% H₂O) hydrogen was used as fuel and stationary air as oxidant. Further, the cell performance was improved when the molar ratio of Fe:Co:Ni approached 1:1:2, i.e. Fe_0.25Co_0.25Ni_0.5. In addition, higher power density and lower interfacial resistance were obtained for cells with the Fe_0.25Co_0.25Ni_0.5-SDC anodes comparing to that with Ni-SDC anodes, which have been usually used for LT-SOFCs. The promising performance of Fe_xCo_0.5−xNi_0.5 as anodes suggests that trimetallic anodes are worth considering for SOFCs that operate at low-temperature.     

Structural and magnetic characterization of MnxZn1 − xFe2O4 (x = 0.2; 0.35; 0.65; 0.8; 1.0) ferrites obtained by the citrate precursor method

In this work the microstructure and magnetic properties of Mn-Zn ferrites powders were investigated. Mn_xZn1 _− xFe₂O₄ powders where x = 0.2; 0.35; 0.5; 0.65; 0.8 and 1.0 were obtained by citrate precursor method. Citrate resin precursor was burned on air atmosphere at 400 °C for 3 h. Mn-Zn powders were calcined at 950 °C during 150 min under inert atmospheres: N₂ and rarefied atmosphere. Thermal analysis of precursor resin, phase evolution and microstructure of Mn-Zn ferrites powders were investigated by TG, DTA, XRD and SEM techniques. The powders calcined under rarefied atmosphere show spinel cubic structure and contamination of α-Fe₂O₃, while powders calcined under N₂ presents only the spinel cubic structure. Particle size was observed by SEM ranging from 80 to 150 nm. The magnetic properties were measured employing a vibrating sample magnetometer (VSM). It was observed that the saturation magnetization M_s increased with the increase of Mn content. The M_s of Mn_0.8Zn_0.2Fe₂O₄ calcined on rarefied atmosphere and Mn_0.8Zn_0.2Fe₂O₄ calcined on N₂ was 23.31 emu g⁻¹ and 56.23 emu g⁻¹, respectively.     

Re-examination of bulk and grain boundary conductivities of Ce1−xGdxO2−δ ceramics

Powders of gadolinium-doped ceria solid solutions, Ce_1−xGd_xO_2−δ (x = 0.05, 0.1, 0.2, 0.3 and 0.4), were prepared by a freeze-drying precursor route. Dense ceramic pellets with average grain sizes in the range of several microns were obtained after sintering at 1600 °C. Cobalt nitrate was added to the powders to obtain dense ceramic samples with grain sizes in the submicrometer range at 1150 °C. The ionic conduction was analysed by impedance spectroscopy in air, to de-convolute the bulk and grain boundary contributions. The bulk conductivity at low temperature clearly decreases with increasing content of Gd whereas the activation energy increases. An alternative method is proposed to analyse the extent of defect interactions on conduction. For samples without addition of Co, the specific grain boundary conductivity increases with increasing Gd content. Addition of cobalt does not alter the bulk properties but produces an important increase in the specific grain boundary conductivity, mainly in samples with lower Gd-concentration (x = 0.05 and 0.1). Segregation of Gd and its strong interaction with charge carriers may explain the blocking effects of grain boundaries.