Anders Palmqvist

Large thermoelectric figure of merit at high temperature in Czochralski-grown clathrate Ba8Ga16Ge30

The Czochralski method was used to grow a 46-mm-long crystal of the Ba8Ga16Ge30 clathrate, which was cut into disks that were evaluated for thermoelectric performance. The Seebeck coefficient and electrical and thermal conductivities all showed evidence of a transition from extrinsic to intrinsic behavior in the range of 600–900K. The corresponding figure of merit (ZT) was found to be a record high of 1.35 at 900K and with an extrapolated maximum of 1.63 at 1100K. This makes the Ba8Ga16Ge30 clathrate an exceptionally strong candidate for medium and high-temperature thermoelectric applications.

Synthesis of ordered mesoporous materials using surfactant liquid crystals or micellar solutions

Abstract Formation of ordered mesoporous materials using surfactant templating proceeds via mechanisms relying on optimising interactions between the inorganic and organic components of the synthesis. For oxides, the rates of hydrolysis and condensation of the inorganic species relative the rate of assembly of the mesostructure is crucial. Synthetic strategies to control these factors have been reviewed and it appears that mesostructured silica can be prepared in most phases found in binary surfactant–water systems by optimising the volume fraction of the surfactant and the hydrolysed inorganic precursor.

Selective catalytic reduction of NOx with NH3 over zeolite H–ZSM-5: influence of transient ammonia supply

The effect of ammonia supply on the selective catalytic reduction of NOX over zeolite H-ZSM-5 was investigated using step response experiments between 200 and 500 degrees C. For inlet NO:NO2 ratios > 1, the activity for NOX reduction transiently increased when NH3 was removed from the feed. For NO:NO2 ratios less than or equal to 1, the NOX reduction however decreased. By pulsing NH3 to the feed, the activity for NO reduction was enhanced up to five times compared to continuous supply of ammonia. For NO:NO2 ratios exceeding one, also the selectivity towards N2O formation was lower with transient ammonia supply. Temperature programmed reaction experiments with preadsorbed NH3 showed highest initial NOX reduction activity when ammonia had been adsorbed at 300 or 250 degrees C compared to 200 degrees C. A minimum in NO reduction was observed at 130 degrees C independent of the ammonia adsorption temperature. For NO:NO2 ratios > 1, the results strongly indicate that NO oxidation is the rate determining step in the ammonia selective catalytic reduction (NH3-SCR) reaction over H-ZSM-5.

Surfactant-templated mesostructured materials from inorganic silica

Mesoporous silica materials made by the use of self-assembled surfactants as templates have attracted a lot of interest in recent years. The number of publications on the topic has increased by a factor of 100 between 1993 and 2003. The vast majority of the papers deal with syntheses from organosilicates, such as tetramethylorthosilicate (TMOS) and tetraethylorthosilicate (TEOS), as the silica source. These alkoxides are convenient as a starting material but they are expensive and the products made from them can only find use in applications where price is not a major issue. This review summarizes the published work on the preparation of mesoporous silica from inorganic sources, such as water glass and silica sol, still using self-assembled surfactants as the template. The use of such raw materials instead of the organosilicates will radically change the production price of the products and may open up completely new fields of application. Much less work has been put into the synthesis of mesoporous silica from these starting materials and relatively little is known about the reaction mechanism. The current understanding is summarized and discussed and comparisons are made with the conventional route that originates from the organosilicates.

Enhanced thermoelectric properties of Mg2Si by addition of TiO2 nanoparticles

The effects on the thermoelectric properties of Mg2Si when adding TiO2 nanoparticles have been evaluated experimentally. A batch of Mg2Si was prepared through direct solid state reaction and divided into portions which were mechanically mixed with different amounts of TiO2 nanoparticles ranging from 0.5 to 3 vol% and subsequently sintered to disks. All materials showed n-type conduction and the absolute value of the Seebeck coefficient was reduced with increasing amount of TiO2 added, while the electrical resistivity was greatly reduced. The thermal conductivity was surprisingly little affected by the addition of the nanoparticles. An optimum value of the thermoelectric figure-of-merit ZT = TS2 sigma/k was found for the addition of 1 vol% TiO2, showing almost three times higher ZT value than that of the pure Mg2Si. Larger TiO2 additions resulted in lower ZT values and with 3 vol% added TiO2 the ZT was comparable to the pure Mg2Si. The sintering process resulted in reduction or chemical reaction of all TiO2 to TiSi2 and possibly elemental titanium as well as reduced TiOx. The increased electrical conductivity and the decreased Seebeck coefficient were found due to an increased charge carrier concentration, likely caused by the included compounds or titanium-doping of the Mg2Si matrix. The low observed effect on the thermal conductivity of the composites may be explained by the relatively higher thermal conductivity of the included compounds, counter-balancing the expected increased grain boundary scattering. Alternatively, the introduction of compounds does not significantly increase the concentration of scattering grain boundaries.

The influence of CO2, C3H6, NO, H2, H2O or SO2 on the low-temperature oxidation of CO on a cobalt-aluminate spinel catalyst (Co1.66Al1.34O4)

A preparation method for making a high temperature stable monolith catalyst, using a cobalt-rich cobalt-aluminate spinel (Co1.66Al1.34O4) as the active material, is proposed. This catalyst, which is known for being active for CO oxidation at low temperatures, was prepared and characterised by BET, SEM, XRD, XPS and CO-TPD. The catalyst was tested for its capacity to oxidise carbon monoxide using oxygen only and oxygen in combination with other compounds typically present in cold start exhausts from Otto engines, i.e. CO2, C3H6. NO, H2, H2O or SO2. When the catalytic activity was tested with only CO and O-2 present in the feed gas, complete conversion was reached at room temperature. When other compounds were present in the gas mixture, they inhibited the CO oxidation to various degrees. The degree of inhibition for the compounds investigated was found to be: SO2 > H2O > NO = C3H6 > H2 > CO2. The main reason for the loss of activity is suggested to origin from the compounds adsorption and formation of different species on the cobalt oxide surface, which seems to inhibit the reduction and/or re-oxidation process of the metal oxide surface and/or the adsorption of CO.

Low‐Cost High‐Performance Zinc Antimonide Thin Films for Thermoelectric Applications

Zinc antimonide thin films with high thermoelectric performance are produced by a simple sputtering method. The phase-pure Zn(4)Sb(3) and ZnSb thin films fulfill the key requirements for commercial TE power generation: cheap elements, cheap fabrication method, high performance and thermal stability. In addition, two completely new meta-stable crystalline phases of zinc antimonide have been discovered.

Composite thermoelectric materials with embedded nanoparticles

The current status of the development of composite thermoelectric materials with embedded nanoparticles is reviewed. An introduction is given to the suggested mechanisms of improving thermoelectric properties by inclusions of nanoparticles and to experimental methods used to prepare such composites. The progress made in the development of thermoelectric materials with embedded nanoparticles is then covered, grouping the studies according to the optimal temperature range of operation of the materials investigated. Most studies have been devoted to materials within the medium temperature range, followed by low temperature materials, whereas high temperature materials have not yet received much attention within this area. In the majority of the materials systems studied, reports of improved thermoelectric performance upon introduction of nanoparticles in bulk thermoelectrics are found. However, for continued progress in this area, there is a need for systematic experimental studies that unambiguously correlate the resulting physical effects of the nanoinclusions to the measured materials properties.

Thermal stability and thermoelectric properties of p-type Ba8Ga16Ge30 clathrates

The thermal stability of p-type Ba(8)Ga(16)Ge(3)0 clathrates grown from gallium flux has been tested by heat treatment in low pressure Ar atmosphere at 400, 600, and 800 degrees C. Significant gallium loss was observed for all samples during heat treatment. The treatment at 400 degrees C does not significantly change the sample properties, and the samples remain p-type and comparable to the untreated, as-prepared, sample. At 600 degrees C the sample switches from extrinsic p-type to extrinsic n-type, presumably due to significant loss of Ga, and shows a high thermopower but a reduced electrical conductivity compared to as-made n-type samples. Surprisingly, after a thermal treatment at 800 degrees C, the crystal structure seemingly loses less Ga, only reducing the hole concentration to near intrinsic levels and thus has a negative impact on ZT. Regardless of the heat treatment temperature of the p-type samples the thermal conductivity remained exceptionally low, for some samples 0.9 W/m K. Heat treatment can thus greatly affect the thermoelectric properties of p-type Ba(8)Ga(16)Ge(3)0, but the crystal structure remains intact

Study of the pluronic-silica interaction in synthesis of mesoporous silica under mild acidic conditions.

The interaction between silica and poly(ethylene oxide) (PEO) in water may appear trivial and it is generally stated that hydrogen bonding is responsible for the attraction. However, a literature search shows that there is not a consensus with respect to the mechanism behind the attractive interaction. Several papers claim that only hydrogen bonding is not sufficient to explain the binding. The silica-PEO interaction is interesting from an academic perspective and it is also exploited in the preparation of mesoporous silica, a material of considerable current interest. This study concerns the very early stage of synthesis of mesoporous silica under mild acidic conditions, pH 2-5, and the aim is to shed light on the interaction between silica and the PEO-containing structure directing agent. The synthesis comprises two steps. An organic silica source, tetraethylorthosilicate (TEOS), is first hydrolyzed and Pluronic P123, a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymer, is subsequently added at different time periods following the hydrolysis of TEOS. It is shown that the interaction between the silica and the Pluronic is dependent both on the temperature and on the time between onset of TEOS hydrolysis and addition of the copolymer. The results show that the interaction is mainly driven by entropy. The effect of the synthesis temperature and of the time between hydrolysis and addition of the copolymer on the final material is also studied. The material with the highest degree of mesoorder was obtained when the reaction was performed at 20 degrees C and the copolymer was added 40 h after the start of TEOS hydrolysis. It is claimed that the reason for the good ordering of the silica is that whereas particle formation under these conditions is fast, the rate of silica condensation is relatively low.