The Effect of Grain Size and Density on the Thermoelectric Properties of Bi2Te3-PbTe Compounds

The effects of microstructure on thermoelectric properties were investigated in Bi₂Te₃-PbTe compounds of different grain size and density. Powders of two different sizes [0.1 μm to 1 μm (micropowder) and <50 nm (nanopowder)] were prepared from Bi₂Te₃-PbTe ingots by ball milling and high-energy ball milling. Three different samples were spark plasma sintered from each powder and the mixture of the two powders. The grain size and relative density of the sintered samples varied from 100 nm to a few micrometers and 89.7% to 97.3%, respectively. The dimensionless figure of merit zT of the sample sintered from nanopowder was about 0.50 at 500 K, being about 3.3 times larger than that of the sample sintered from micropowder (～0.15 at 500 K), when the relative density of the former and the latter were 89.7% and 97.3%, respectively. The improved thermoelectric performance of the samples may originate from the decrease of the thermal conductivity, which was caused by the decrease of the grain size and the increase of the amount of pores.     

机械力化学作用对低介硅灰石瓷料的相变和相组成的影响

采用X射线衍射仪(XRD)、差热分析(DTA)手段详细研究了由氧化物粉末制备硅灰石陶瓷时,机械力化学作用及后续热处理对硅灰石陶瓷相组成和相变过程的影响,分析了机械力化学在球磨过程中的作用机理主要是细化晶粒、使晶格畸变、晶格缺陷增多、非晶化和诱导低温化学反应。结果表明:高能球磨中的机械力化学作用能够有效地降低硅灰石陶瓷的烧成温度(11160~11220℃)。探明了经高能球磨的样品在烧成过程中的晶相转变规律。瓷料最终的晶相为单一的-硅灰石(高温变体)。     

Synthesis and Characterization of Al-Doped Mg2Si Thermoelectric Materials

Magnesium silicide (Mg₂Si)-based alloys are promising candidates for thermoelectric (TE) energy conversion for the middle to high range of temperature. These materials are very attractive for TE research because of the abundance of their constituent elements in the Earth’s crust. Mg₂Si could replace lead-based TE materials, due to its low cost, nontoxicity, and low density. In this work, the role of aluminum doping (Mg₂Si:Al = 1:x for x = 0.005, 0.01, 0.02, and 0.04 molar ratio) in dense Mg₂Si materials was investigated. The synthesis process was performed by planetary milling under inert atmosphere starting from commercial Mg₂Si pieces and Al powder. After ball milling, the samples were sintered by means of spark plasma sintering to density >95%. The morphology, composition, and crystal structure of the samples were characterized by field-emission scanning electron microscopy, energy-dispersive spectroscopy, and x-ray diffraction analyses. Moreover, Seebeck coefficient analyses, as well as electrical and thermal conductivity measurements were performed for all samples up to 600°C. The resultant estimated ZT values are comparable to those reported in the literature for these materials. In particular, the maximum ZT achieved was 0.50 for the x = 0.01 Al-doped sample at 600°C.     

Effects of Carbon Coating on Microstructure and Dielectric Properties of CaCu3Ti4O12

CaCu₃Ti₄O₁₂ (CCTO) powders coated with carbon were synthesized by using a high-energy ball milling method. The obtained samples were characterized by x-ray diffraction, transmission electron microscopy and scanning electron microscopy. The carbon-coated CCTO particles had a rough surface, which resulted from the growth of the carbon coating on the CCTO particles. It was found that the CCTO phase was observed as the major phase and no reaction occurred between the carbon and CCTO during the sintering process. The grain size of the CCTO ceramics decreased with the increase in carbon content, which indicated that carbon inhibits grain growth of CCTO ceramics. Specially, the dielectric constant decreased with the increase in carbon content. And CCTO1 ceramic (mass ratio of CCTO: carbon = 10:1) showed a lower dielectric constant (3.74 × 10⁴), with the dielectric loss value (0.04) much lower than that of CCTO at 20°C (10 k Hz).     

球磨与共沉淀法制备MnZn铁氧体的对比研究

分别采用高能球磨和化学共沉淀法制备了MnZn铁氧体,通过XRD、VSM和金相显微镜的分析,对两种铁氧体的预烧料粉末、烧结体的显微结构以及磁性能做了比较。结果表明:化学共沉淀法所制备的预烧料粉末具有晶粒细小、均匀和活性高等优点;与高能球磨法相比,化学共沉淀法烧结磁体的密度较高、晶粒尺寸较大,磁性能更为优良。其相应的磁性能参数Ms、Mr、Hc和μi分别为3.845×102kA/m,3.421kA/m,0.722kA/m和5500。     

Development of a Thermoelectric Module Using the Heusler Alloy Fe<Subscript>2</Subscript>VAl

A thermoelectric module was constructed using a Heusler Fe₂VAl sintered alloy prepared by pulse-current sintering (PCS) using mechanically alloyed powder. A large-amplitude vibration mill was developed for powder preparation. The processing rate was increased 50-fold over that of laboratory planetary ball milling. In all, 25 pieces of millimeter-sized sintered alloy, which is useful for thermoelectric devices without cutting, were fabricated simultaneously using a single PCS process. The thermoelectric module consisting of the high-strength sintered alloy and electrode joint showed high durability. This module stably generated electric power on the exhaust pipe of a running motorcycle.     

Fabrication of Metallic Glass Powder for Brazing Paste for High-Temperature Thermoelectric Modules

Metallic glass (MG) offers the advantage of outstanding oxidation resistance, since it has disordered atomic-scale structure without grain boundaries. We fabricated Al-based MG ribbons (Al_84.5Y₁₀Ni_5.5) by a melt spinning process. We evaluated the adhesion strength of interfaces between the Al-based MG and a Ni-coated Cu electrode formed under various conditions at high temperature. In addition, we attempted to optimize the process conditions for pulverizing MG ribbons to < 100 micrometers by combining high-energy ball milling and planetary milling. We confirmed that the electrical resistivity of the Al-based MG ribbon was substantially reduced after annealing at high temperature (over 300°C) due to crystallization.     

Ultrahigh Energy‐Storage Density in Antiferroelectric Ceramics with Field‐Induced Multiphase Transitions

The excellent energy‐storage performance of ceramic capacitors, such as high‐power density, fast discharge speed, and the ability to operate over a broad temperature range, gives rise to their wide applications in different energy‐storage devices. In this work, the (Pb_0.98La_0.02)(Zr_0.55Sn_0.45)_0.995O₃ (PLZS) antiferroelectric (AFE) ceramics are prepared via a unique rolling machine approach. The field‐induced multiphase transitions are observed in polarization–electric field (P–E) hysteresis loops. All the PLZS AFE ceramics possess high energy‐storage densities and discharge efficiency (above 80%) with different sintering temperatures. Of particular significance is that an ultrahigh recoverable energy‐storage density of 10.4 J cm^‐3 and a high discharge efficiency of 87% are achieved at 40 kV mm^‐1 for PLZS ceramic with a thickness of 0.11 mm, sintered at 1175 °C, which are by far the highest values ever reported in bulk ceramics. Moreover, the corresponding ceramics exhibit a superior discharge current density of 1640 A cm^‐2 and ultrafast discharge speed (75 ns discharge period). This great improvement in energy‐storage performance is expected to expand the practical applications of dielectric ceramics in numerous electronic devices.     

纳米添加剂对永磁铁氧体微结构与性能的影响

通过高能球磨将添加剂纳米化,研究了其对永磁铁氧体(样品)磁性能和微观结构的影响。结果表明:添加剂的平均粒度从216.448μm减小到65nm时,有效降低了磁体的熔点,提高其致密化。1190℃烧结时磁体的Br和Hcj分别从404mT、366kA·m–1提高到418mT和402kA·m–1。SEM观察样品晶粒平均粒径在1~2μm,晶粒分布更加均匀。取向度从75.2%提高到84.0%。     

Solid-state synthesis of modified (Bi0.5Na0.5)TiO3 piezoelectric nanocrystalline ceramics and evaluating their properties

The piezoelectric nanocrystalline ceramics of (Bi_0.5Na_0.5) TiO₃, 0.94(Bi_0.5Na_0.5) TiO₃–0.06BaTiO₃, 0.82(Bi_0.5Na_0.5) TiO₃–0.18(Bi_0.5K_0.5) TiO₃ and 0.85(Bi_0.5Na_0.5) TiO₃–0.144(Bi_0.5K_0.5)TiO₃–0.006BaTiO₃ (abbreviated as BNT, BNBT6, BNKT18 and BNT–BT–BKT, respectively) have been synthesized by a modified solid state approach using high-energy planetary ball-milling. The crystal structures of ceramics were determined using X-ray diffraction (XRD) method and that the microstructures as well as the morphology of the sintered ceramic specimens were observed using scanning-electron microscopy (SEM). The dielectric coefficient was also calculated based on its relation with a constant capacitance measured by an electrical circuit on the basis of the Wetston–Bridge and the piezoelectric coefficient (d₃₃) measured with a d₃₃-meter. On the calcination of powders the XRD results showed that the perovskite phase was formed perfectly and the crystallite sizes of BNT, BNBT6, BNKT18 and BNT–BT–BKT were estimated at about >100, 55, 36 and 63 nm, respectively. Also, the crystallite sizes of the calcinated BNT powders over the course of 5, 10, 20, 30 and 40 h of ball-milling were estimated at about 86, 82, 72, 53, 81 nm, respectively. Moreover, the results of XRD and SEM analysis of the sintered powders at 750–1150 °C confirmed the positive effect of nanocrystalline formation during ball-milling in decreasing the sintering temperature and increasing the density of the sintered samples. Furthermore, electrical calculations such as dielectric and piezoelectric coefficients showed that the modified BNKT18 nanocrystalline ceramic sintered at 1150 °C was to have the best values of dielectric (ε_r=792 at 1 kHz) and piezoelectric coefficients (d₃₃=85.9 pC/N) in comparison with the other synthesized piezoelectric ceramics.     

Low-Temperature Processing of PZT Thick Film by Seeding and High-Energy Ball Milling and Studies on Electrical Properties

Lead zirconate titanate thick film with molecular formula PbZr_0.52Ti_0.42O₃ (PZT) was prepared by a modified conventional sol–gel method through seeding and high-energy ball milling, resulting in perovskite phase formation at lower temperatures. The ball-milling time was optimized by keeping the seed particle loading (5 wt.%) constant in the sol–gel solution. This methodology helped in reduction of the crystalline phase formation temperature to 300°C, which is much lower than that reported in the literature (450°C). The well-established perovskite phase was confirmed by x-ray diffraction (XRD) analysis. Scanning electron microscopy (SEM) of PZT films revealed uniform and crystalline microstructure. Film prepared by this methodology showed higher spontaneous polarization (2.22 μC/cm²), higher capacitance (1.17 nF), and low leakage current density (18 μA/cm²). The results obtained from ferroelectric characterization showed a strong correlation with the XRD and SEM results.     

Effect of Synthesis and Sintering Conditions on the Thermoelectric Properties of n-Doped Mg2Si

Magnesium silicide (Mg₂Si)-based alloys are promising candidates for thermoelectric (TE) energy conversion in the middle–high temperature range. The detrimental effect of the presence of MgO on the TE properties of Mg₂Si based materials is widely known. For this reason, the conditions used for synthesis and sintering were optimized to limit oxygen contamination. The effect of Bi doping on the TE performance of dense Mg₂Si materials was also investigated. Synthesis was performed by ball milling in an inert atmosphere starting from commercial Mg₂Si powder and Bi powder. The samples were consolidated, by spark plasma sintering, to a density >95%. The morphology, and the composition and crystal structure of samples were characterized by field-emission scanning electronic microscopy and x-ray diffraction, respectively. Moreover, determination of Seebeck coefficients and measurement of electrical and thermal conductivity were performed for all the samples. Mg₂Si with 0.1 mol% Bi doping had a ZT value of 0.81, indicative of the potential of this method for fabrication of n-type bulk material with good TE performance.     

Preparation and characterization of bronze/SiCp composites produced via current activated sintering method

In this study, bronze matrix was reinforced with nickel coated nano SiC particles using mechanical alloying and then subsequent rapid current sintering technique. Mechanical ball milling of bronze matrix composite powders were performed with 1.0, 3.0 and 5.0 vol% SiC nanoparticle reinforcements. The composite powders were cold compacted under constant pressure of 150 MPa. The compacted structures were sintered at atmospheric conditions almost to the full density within 10 min using current sintering, in which the powders were heated by a low voltage and high amperage current and compressed simultaneously to achieve dispersion of nano SiC particles. The samples were sintered at 900 A current to eliminate porosities and agglomeration of particles. The porosity of the produced samples were reduced from 9.49% to 6.13% respectively for the uncoated and coated 5.0 vol% SiC reinforced nanocomposites. Microhardness testing and scanning electron microscopy (SEM) were used for the microstructural characterization of the composites. Rapid sintering was also thought to be an advantage to eliminate volume increment seen under conventional atmospheric sintering conditions.     

Dielectric Properties in the Microwave Range of K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>NbO<Subscript>3</Subscript> Ceramics

Dielectric properties of a potassium sodium niobate (KNN) system in the microwave range up to GHz have rarely been studied. Since K_0.5Na_0.5NbO₃ is the most common and typical type of KNN materials, non-doped K_0.5Na_0.5 NbO₃ ceramics were synthesized at different temperatures (1080°C, 1090°C, 1100°C, and 1110°C) by a traditional solid reaction method for further characterization and analysis. The ceramics were in perovskite phase with orthorhombic symmetry. A small quantity of second phase was found in the 1110°C sintered specimen, which resulted from the volatilization of alkali oxides as the temperature increased. The complex permittivity was measured for the first time in the microwave range (8.2–12.4 GHz) and in the temperature range from 100°C to 220°C, and the effects of annealing on the dielectric properties were studied. The results indicate that the complex permittivity of KNN ceramics over the microwave range increases mainly due to high bulk density and the additional dielectric contributions of oxygen vacancies at high temperature.     

激光烧结锆钛酸钡压电陶瓷

报道了采用激光烧结技术制备锆钛酸钡(BZT)压电陶瓷的研究。用常规方法制备了锆钛酸钡粉料，采用CO2激光直接烧结锆钛酸钡坯材，最大激光功率150 W，扫描转速1440 rad/min，烧结时间10 min;对陶瓷样品介电频谱与谐振频谱的测量显示了锆钛酸钡的压电特征;比较了传统高温炉烧结与激光烧结陶瓷样品的高温介电谱线，激光烧结陶瓷样品居里温度有所提高;测得介电常数和压电常数分别为1563 pC/N和45pC/N;X射线衍射(XRD)谱图显示(111),(002)衍射峰相对强度增强;陶瓷样品表面的显微照片显示了晶粒生长的形貌。激光烧结可以作为功能陶瓷烧结的方法之一。     

Effect of Transition-Metal Additives on Thermoelectric Properties of YB<Subscript>22</Subscript>C<Subscript>2</Subscript>N

The higher boride compound YB₂₂C₂N has been reported as a promising n-type high-temperature thermoelectric material and possible counterpart to boron carbide. To investigate the influence of transition-metal additives on the thermoelectric properties of YB₂₂C₂N, a series of Rh, Co, Cu, and Ni samples were prepared. The resistivity and Seebeck coefficient of the samples were measured in the temperature range of 323 K to 1073 K. Samples with Rh and Co additives showed a considerable reduction of resistivity in comparison with pure YB₂₂C₂N and maintained their semiconducting properties at high temperatures. A sample with Co, obtained using long-term ball milling, showed the highest absolute value of Seebeck coefficient among all previously studied YB₂₂C₂N-based materials. Analyses of the influence of transition-metal additives and processing methods such as ball milling on the thermoelectric properties of YB₂₂C₂N are presented.     

Mechanical Alloying and Spark Plasma Sintering of Higher Manganese Silicides for Thermoelectric Applications

The present challenges in the energy crisis require finding new ways to reduce consumption of fossil fuels. Thermoelectrics can help reduce fuel consumption by producing electricity from waste heat. The higher manganese silicides (HMS) have shown promise in this field as inexpensive, nontoxic, and highly stable p-type thermoelectric materials. One of the production techniques for HMS is mechanical alloying by ball milling. In this research the effect of the ball-milling duration and speed on the phases produced was studied. Mn and Si powders were milled at speeds of 200 RPM to 800 RPM for 1 h to 7 h. X-ray diffraction (XRD) results of the samples prepared using mechanical alloying show deterioration into the MnSi phase. The sample that underwent 5 h of milling at 800 RPM showed the greatest amount of HMS phase and was subsequently spark plasma sintered. The sample showed insufficient thermoelectric properties (ZT ≈ 0.1 at 450°C), compared with either solid-state reaction samples showing ZT ≈ 0.4 or cast samples showing ZT ≈ 0.63 at 450°C. The reduced ZT values of the mechanically alloyed and spark-plasma-sintered samples were attributed to the high relative amount of MnSi phase. The correlation between the relative amount of MnSi and the transport properties is described in detail.     

Enhancement-mode In0.53Ga0.47As metal-oxide-semiconductor field-effect transistors with sol–gel processed gate dielectrics

Enhancement-mode In_0.53Ga_0.47As n-type metal-oxide-semiconductor field-effect transistors (MOSFETs), with barium zirconate titanate (BZT) and titanium dioxide (TiO₂) high-κ materials prepared via the solution–gelation process as gate dielectrics, have been fabricated. The dielectric constants of BZT and TiO₂ are 6.67 and 19.3, respectively. The In_0.53Ga_0.47As MOSFET with TiO₂ exhibits better electrical characteristics than the In_0.53Ga_0.47As MOSFET with BZT. These characteristics include higher maximum drain current density, higher maximum transconductance, and smaller subthreshold swing.     

A Novel Approach to BaTiO3-based X8R Ceramics by Calcium Borosilicate Glass Ceramic Doping

High-performance X8R dielectric materials could be sintered at 1150°C by doping calcium borosilicate (CBS) glass ceramic into the BaTiO₃-Nb₂O₅-ZnO system, with a dielectric constant greater than 1800 and a dielectric loss lower than 1.0%. The effects of CBS, Nb₂O₅, and ZnO on the dielectric properties were discussed in this article. The X8R specification was achieved with the content of CBS ≥ 4 wt.%, Nb₂O₅ ≥ 1.0 mol%, and ZnO ≤ 2.0 mol%. The sample doped with 4 wt.% CBS exhibited the highest density and lowest dielectric loss in our experiment. A reduction in grain size was observed in the specimens with 4 and 7 wt.% CBS as compared with CBS-free specimen, whereas the abnormal growth of rectangle-shaped grains took place in the 10 wt.% CBS-doped specimen. The Curie point progressively moved to higher temperatures with CBS content up to 7 wt.%. However, T _c of the sample decreased slightly in the case when 10 wt.% CBS was doped. X-ray diffraction (XRD) analysis indicated that the crystal structure of sintered ceramics changed from tetragonal to pseudocubic symmetry as increasing CBS content.     

Ball Mill Synthesis of Bulk Quaternary Cu<Subscript>2</Subscript>ZnSnSe<Subscript>4</Subscript> and Thermoelectric Studies

In this work, quaternary chalcogenide Cu₂ZnSnSe₄ (CZTSe) was synthesized using a mechanochemical ball milling process and its thermoelectric properties were studied by electrical resistivity, Seebeck coefficient, and thermal conductivity measurements. The synthesis process comprises three steps viz., wet ball milling of the elemental precursors, vacuum annealing, and densification by hot pressing. The purpose of this is to evaluate the feasibility of introducing wet milling in place of vacuum melting in solid state synthesis for the reaction of starting elements. We report the structural characterization and thermoelectric studies conducted on samples that were milled at 300 rpm and 500 rpm. X-ray diffraction (XRD) analysis showed the existence of multiple phases in the as-milled samples, indicating the requirement for heat treatment. Therefore, the ball milled powders were cold pressed and vacuum annealed to eliminate the secondary phases. Annealed samples were hot pressed and made into dense pellets for further investigations. In addition to XRD, energy dispersive spectroscopy (EDS) studies were performed on hot pressed samples to study the composition. XRD and EDS studies confirm CZTSe phase formation along with ZnSe secondary phase. Electrical resistivity and Seebeck coefficient measurements were done on the hot pressed samples in the temperature range 340–670 K to understand the thermoelectric behaviour. Thermal conductivity was calculated from the specific heat capacity and thermal diffusivity values. The thermoelectric figure of merit zT values for samples milled at 300 rpm and 500 rpm are ～0.15 and ～0.16, respectively, at 630 K, which is in good agreement with the values reported for solid state synthesized compounds.