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Sehirlioglu, Alp

Publications and source records attributed to Sehirlioglu, Alp.

At least 19 records

Creating High Temperature Ferroelectrics by Using Ternary Components with Limited Solubility

High temperature ferroelectrics are needed for actuator applications ranging from drilling on the surface of Venus to fuel modulation in jet engines. Machine learning in previous work has dramatically reduced search space and produced new candidates for experimentation. It is possible to create high temperature piezoelectrics by changing the end member of ternary systems. The starting point was near the morphotropic phas boundary between BiScO3(BS) and PbTiO3 (PT) (38%/62%). The third end member was suggested by machine learning to create a high Tc with limited solubility; BiCo0.88Fe0.12O3 (BCF).

Hirt, Benjamin

Freeze Casting of LAGP for 3D Textured Solid-State Structural Electrolytes

In this study, all-solid-state structural lithium-ion batteries, a type of load bearing electrochemical energy storage that provides systems-level weight savings is being pursued for the realization of inherently safe next generation hybrid-electric and all-electric green aerospace propulsion systems. Currently investigated all-solid-state batteries do not meet the requirements for specific power and mechanical stability. To address these issues, freeze casting of lithium aluminum germanium phosphate (LAGP) electrolyte material has been explored for the creation of a textured 3D electrolyte scaffold with large interfacial surface area for high power discharge and hierarchical porosity for accommodation of active material volume changes during electrochemical cycling. We report the effects of freeze casting processing parameters on the microstructural development and mechanical performance of the scaffolds, characterized through scanning electron microscopy and ring-on-ring mechanical testing. Slurry composition and casting parameters such as solids loading, casting speed, tape angle, and temperature gradients have been modified to determine the impact on density, lamellar morphology, and final load-bearing performance.

ceramics

Sintered Cathodes for All-Solid-State Structural Lithium-Ion Batteries

All-solid-state structural lithium ion batteries serve as both structural load-bearing components and as electrical energy storage devices to achieve system level weight savings in aerospace and other transportation applications. This multifunctional design goal is critical for the realization of next generation hybrid or all-electric propulsion systems. Additionally, transitioning to solid state technology improves upon battery safety from previous volatile architectures. This research established baseline solid state processing conditions and performance benchmarks for intercalation-type layered oxide materials for multifunctional application. Under consideration were lithium cobalt oxide and lithium nickel manganese cobalt oxide. Pertinent characteristics such as electrical conductivity, strength, chemical stability, and microstructure were characterized for future application in all-solid-state structural battery cathodes. The study includes characterization by XRD, ICP, SEM, ring-on-ring mechanical testing, and electrical impedance spectroscopy to elucidate optimal processing parameters, material characteristics, and multifunctional performance benchmarks. These findings provide initial conditions for implementing existing cathode materials in load bearing applications.

Ceramics

Filled Nd(sub z) Fe(sub x) Co(sub 4-x) Sb(sub 12-y) Ge(sub y) Skutterudites: Processing and Thermoelectric Properties

Skutterudites have proven to be a useful thermoelectric system as a result of their enhanced figure of merit (ZT1), cheap material cost, favorable mechanical properties, and good thermal stability. The majority of skutterudite interest in recent years has been focused on binary skutterudites like CoSb3. Binary skutterudites are often double and triple filled, with a range of elements from the lanthanide series, in order to reduce the lattice component of thermal conductivity. Ternary and quaternary skutterudites, such as Co4Ge6Se6 or Ni4Sb8Sn4, provide additional paths to tune the electronic structure. The thermal conductivity can further be improved in these complex skutterudites by the introduction of fillers. The Nd (sub z) Fe (sub x) Co (sub 4-x) Sb (sub 12-y)Ge (sub y) system has been investigated as a p-type thermoelectric material, and is stable up to 600 degrees Centigrade. The influence of Fe and Ge content, along with filler Nd, was investigated on thermoelectric transport properties. In addition to the chemical influence on properties, some processing details of the system will also be addressed.

Electical Conductivity

Filled Nd(z)Fe(x)Co(4-x)Sb(12-y)Ge(y) Skutterudites: Processing and Thermoelectric Properties

Skutterudites have proven to be a useful thermoelectric system as a result of their enhanced figure of merit (ZT1), cheap material cost, favorable mechanical properties, and good thermal stability. The majority of skutterudite interest in recent years has been focused on binary skutterudites like CoSb3. Binary skutterudites are often double and triple filled, with a range of elements from the lanthanide series, in order to reduce the lattice component of thermal conductivity. Ternary and quaternary skutterudites, such as Co4Ge6Se6 or Ni4Sb8Sn4, provide additional paths to tune the electronic structure. The thermal conductivity can further be improved in these complex skutterudites by the introduction of fillers. The Nd(z)Fe(x)Co(4-x)Sb(12-y)Ge(y) system has been investigated as a p-type thermoelectric material, and is stable up to 600 C. The influence of Fe and Ge content, along with filler Nd, was investigated on thermoelectric transport properties. In addition to the chemical influence on properties, some processing details of the system will also be addressed.

Thermoelectric

WSi2 in Si(1-x)Ge(x) Composites: Processing and Thermoelectric Properties

Traditional SiGe thermoelectrics have potential for enhanced figure of merit (ZT) via nano-structuring with a silicide phase, such as WSi2. A second phase of nano-sized silicides can theoretically reduce the lattice component of thermal conductivity without significantly reducing the electrical conductivity. However, experimentally achieving such improvements in line with the theory is complicated by factors such as control of silicide size during sintering, dopant segregation, matrix homogeneity, and sintering kinetics. Samples were prepared using powder metallurgy techniques; including mechano-chemical alloying, via ball milling, and spark plasma sintering for densification. Processing, micro-structural development, and thermoelectric properties will be discussed. Additionally, couple and device level characterization will be introduced.

Thermoelectric Power Generation

Analytic Thermoelectric Couple Modeling: Variable Material Properties and Transient Operation

To gain a deeper understanding of the operation of a thermoelectric couple a set of analytic solutions have been derived for a variable material property couple and a transient couple. Using an analytic approach, as opposed to commonly used numerical techniques, results in a set of useful design guidelines. These guidelines can serve as useful starting conditions for further numerical studies, or can serve as design rules for lab built couples. The analytic modeling considers two cases and accounts for 1) material properties which vary with temperature and 2) transient operation of a couple. The variable material property case was handled by means of an asymptotic expansion, which allows for insight into the influence of temperature dependence on different material properties. The variable property work demonstrated the important fact that materials with identical average Figure of Merits can lead to different conversion efficiencies due to temperature dependence of the properties. The transient couple was investigated through a Greens function approach; several transient boundary conditions were investigated. The transient work introduces several new design considerations which are not captured by the classic steady state analysis. The work helps to assist in designing couples for optimal performance, and also helps assist in material selection.

Seebeck Effect

Filled Co (sub X) Ni (sub 4-x) Sb (sub 12-y) Sn (sub Y) Skutterudites: Processing and Thermoelectric Properties

Skutterudites have proven to be a useful thermoelectric system as a result of their enhanced figure of merit (ZT1), cheap material cost, favorable mechanical properties, and good thermal stability. The majority of skutterudite interest in recent years has been focused on binary skutterudites like CoSb3 or CoAs3. Binary skutterudites are often double and triple filled, with a range of elements from the lanthanide series, in order to reduce the lattice component of thermal conductivity. Ternary and quaternary skutterudites, such as Co4Ge6Se6 or Ni4Sb8Sn4, provide additional paths to tune the electronic structure. The thermal conductivity can further be improved in these complex skutterudites by the introduction of fillers. The Co (sub X) Ni (sub 4-x) Sb (sub 12-y) Sn (sub Y) system has been investigated as both a p- and n-type thermoelectric material, and is stable up to 200 degrees Centigrade. Yb, Ce, and Dy fillers have been introduced into the skutterudite to study the influence of both the type and the quantity of fillers on processing conditions and thermoelectric properties. The system was processed through a multi-step technique that includes solidification, mechano-chemical alloying, and hot pressing which will be discussed along with thermoelectric transport properties.

Thermoelectricity

Thermoelectric properties of Co(x)Ni(4-x)Sb(12-y)Sn(y) ternary skutterudites

Thermoelectric materials based on the skutterudite crystal structure have demonstrated enhanced performance (ZT greater than 1), along with good thermal stability and favorable mechanical properties. Binary skutterudites, with single and multiple fillers, have been intensively studied in recent years. Compared to binary skutterudites, the ternary systems have received less attention, e.g. Ni4Sb8Sn4. Ternary skutterudites are isoelectronic variants of binary skutterudites; cation substitutions appear to be isostructural to their binary analogues. In general, ternary skutterudites exhibit lower thermal conductivity. Ternary systems of Ni4Bi8Ge4, Ni4Sb8Ge4, and Ni4Sb8Sn4 were investigated using combined solidification and sintering steps. Skutterudite formation was not achieved in the Ni4Bi8Ge4 and Ni4Sb8Ge4 systems; skutterudite formation occurred in Ni4Sb8Sn4 system. P-type material was achieved by Co substitution for Ni. Thermoelectric properties were measured from 298 K to 673 K for Ni4Sb8Sn4, Ni4 Sb7Sn5 and Co2Ni2Sb7Sn5. N-type Ni4Sb8Sn4 exhibit the highest figure of merit of 0.1 at 523 K.

Seebeck Effect

Analytic Couple Modeling Introducing Device Design Factor, Fin Factor, Thermal Diffusivity Factor, and Inductance Factor

A set of convenient thermoelectric device solutions have been derived in order to capture a number of factors which are previously only resolved with numerical techniques. The concise conversion efficiency equations derived from governing equations provide intuitive and straight-forward design guidelines. These guidelines allow for better device design without requiring detailed numerical modeling. The analytical modeling accounts for factors such as i) variable temperature boundary conditions, ii) lateral heat transfer, iii) temperature variable material properties, and iv) transient operation. New dimensionless parameters, similar to the figure of merit, are introduced including the device design factor, fin factor, thermal diffusivity factor, and inductance factor. These new device factors allow for the straight-forward description of phenomenon generally only captured with numerical work otherwise. As an example a device design factor of 0.38, which accounts for thermal resistance of the hot and cold shoes, can be used to calculate a conversion efficiency of 2.28 while the ideal conversion efficiency based on figure of merit alone would be 6.15. Likewise an ideal couple with efficiency of 6.15 will be reduced to 5.33 when lateral heat is accounted for with a fin factor of 1.0.

Seebeck effect

Detailed Uncertainty Analysis of the ZEM-3 Measurement System

The measurement of Seebeck coefficient and electrical resistivity are critical to the investigation of all thermoelectric systems. Therefore, it stands that the measurement uncertainty must be well understood to report ZT values which are accurate and trustworthy. A detailed uncertainty analysis of the ZEM-3 measurement system has been performed. The uncertainty analysis calculates error in the electrical resistivity measurement as a result of sample geometry tolerance, probe geometry tolerance, statistical error, and multi-meter uncertainty. The uncertainty on Seebeck coefficient includes probe wire correction factors, statistical error, multi-meter uncertainty, and most importantly the cold-finger effect. The cold-finger effect plagues all potentiometric (four-probe) Seebeck measurement systems, as heat parasitically transfers through thermocouple probes. The effect leads to an asymmetric over-estimation of the Seebeck coefficient. A thermal finite element analysis allows for quantification of the phenomenon, and provides an estimate on the uncertainty of the Seebeck coefficient. The thermoelectric power factor has been found to have an uncertainty of +9-14 at high temperature and 9 near room temperature.

Seebeck effect

Co(x)Ni(4-x)Sb(12-y)Sn(y) Ternary Skutterudites: Processing and Thermoelectric Properties

Skutterudites have proven to be a useful thermoelectric system as a result of their high figure of merit, favorable mechanical properties, and good thermal stability. Binary skutterudites have received the majority of interest in recent years, as a result of successful double and triple filling schemes. Ternary skutterudites, such as Ni4Sb7Sn5, also demonstrate good thermoelectric performance, with high power factor and low thermal conductivity. Ternary skutterudites, as contrasted to binary systems, provide more possibility for tuning electronic structure as substitutions can be studied on three elements. The Co(x)Ni(4-x)Sb(12-y)Sn(y) system has been investigated as both a p- and n-type thermoelectric material, stable up to 200 C. The system is processed through a combination of solidification, mechanical alloying, and hot pressing steps. Rietveld structure refinement has revealed an interesting occupancy of Sn on both the 24g Wyckoff position with Sb as well as the 2a position as a rattler. In addition to thermoelectric properties, detailed processing routes have been investigated on the system.

Seebeck effect

Si-Ge Nano-Structured with Tungsten Silicide Inclusions

Traditional silicon germanium high temperature thermoelectrics have potential for improvements in figure of merit via nano-structuring with a silicide phase. A second phase of nano-sized silicides can theoretically reduce the lattice component of thermal conductivity without significantly reducing the electrical conductivity. However, experimentally achieving such improvements in line with the theory is complicated by factors such as control of silicide size during sintering, dopant segregation, matrix homogeneity, and sintering kinetics. Samples are prepared using powder metallurgy techniques; including mechanochemical alloying via ball milling and spark plasma sintering for densification. In addition to microstructural development, thermal stability of thermoelectric transport properties are reported, as well as couple and device level characterization.

thermoelectricity

High Temperature Ferroelectrics for Actuators: Recent Developments and Challenges

A variety of piezoelectric applications have been driving the research in development of new high temperature ferroelectrics; ranging from broader markets such as fuel and gas modulation and deep well oil drilling to very specific applications such as thermoacoustic engines and ultrasonic drilling on the surface of Venus. The focus has been mostly on increasing the Curie temperature. However, greater challenges for high temperature ferroelectrics limit the operating temperature to levels much below the Curie temperature. These include enhanced loss tangent and dc conductivity at high fields as well as depoling due to thermally activated domain rotation. The initial work by Eitel et al. [Jpn. J. Appl. Phys., 40 [10, Part 1] 59996002 (2001)] increased interest in investigation of Bismuth containing perovskites in solid solution with lead titanate. Issues that arise vary from solubility limits to increased tetragonality; the former one prohibits processing of morphotropic phase boundary, while the latter one impedes thorough poling of the polycrystalline ceramics. This talk will summarize recent advances in development of high temperature piezoelectrics and provide information about challenges encountered as well as the approaches taken to improve the high temperature behavior of ferroelectrics with a focus on applications that employ the converse piezoelectric effect.

Piezoelectric

Transient Thermoelectric Solution Employing Green's Functions

The study works to formulate convenient solutions to the problem of a thermoelectric couple operating under a time varying condition. Transient operation of a thermoelectric will become increasingly common as thermoelectric technology permits applications in an increasing number of uses. A number of terrestrial applications, in contrast to steady-state space applications, can subject devices to time varying conditions. For instance thermoelectrics can be exposed to transient conditions in the automotive industry depending on engine system dynamics along with factors like driving style. In an effort to generalize the thermoelectric solution a Greens function method is used, so that arbitrary time varying boundary and initial conditions may be applied to the system without reformulation. The solution demonstrates that in thermoelectric applications of a transient nature additional factors must be taken into account and optimized. For instance, the materials specific heat and density become critical parameters in addition to the thermal mass of a heat sink or the details of the thermal profile, such as oscillating frequency. The calculations can yield the optimum operating conditions to maximize power output andor efficiency for a given type of device.

thermoelectric power generation

Uncertainty Analysis of Seebeck Coefficient and Electrical Resistivity Characterization

In order to provide a complete description of a materials thermoelectric power factor, in addition to the measured nominal value, an uncertainty interval is required. The uncertainty may contain sources of measurement error including systematic bias error and precision error of a statistical nature. The work focuses specifically on the popular ZEM-3 (Ulvac Technologies) measurement system, but the methods apply to any measurement system. The analysis accounts for sources of systematic error including sample preparation tolerance, measurement probe placement, thermocouple cold-finger effect, and measurement parameters; in addition to including uncertainty of a statistical nature. Complete uncertainty analysis of a measurement system allows for more reliable comparison of measurement data between laboratories.

Seebeck effect

Effects of Dopant on Depoling Temperature in Modified BiScO3 - PbTiO3

In recent years there has been a renewed interest for high temperature piezoelectrics for both terrestrial and aerospace applications. These applications are limited in part by the operating temperature, which is usually taken as one half of the Curie temperature (Tc), and is 200C for one of the most widely used commercial piezoelectrics, Pb(Zr,Ti)O3 (PZT). In an effort to increase Tc, subsequent research into high temperature Bi(BB)O3 PbTiO3 piezoelectrics led to the discovery of the morphotropic phase boundary (MPB) in the high-Tc BiScO3 PbTiO3 (BS-PT) system with a Tc of 460C and a d33 of 460 pmV. The Tc marks the ferroelectric to paraelectric phase transformation and while, in general, a phase transformation leads to thermal depoling in piezoelectrics with low or moderate Tcs, for high Tc piezoelectrics thermally assisted dipole rotation can lead to randomization of domains at temperatures below Tc. It becomes necessary to determine the depoling temperature (Td) which dictates the actual working temperature range. By doping for Sc and Ti the Td can be shifted while maintaining similar electromechanical properties as a function of temperature. The effect of this B-site doping on depoling temperature has been explored through the characterization of microstructure and weakhigh field measurements.

Actuator

Extended Analytic Device Optimization Employing Asymptotic Expansion

Analytic optimization of a thermoelectric junction often introduces several simplifying assumptionsincluding constant material properties, fixed known hot and cold shoe temperatures, and thermallyinsulated leg sides. In fact all of these simplifications will have an effect on device performance,ranging from negligible to significant depending on conditions. Numerical methods, such as FiniteElement Analysis or iterative techniques, are often used to perform more detailed analysis andaccount for these simplifications. While numerical methods may stand as a suitable solution scheme,they are weak in gaining physical understanding and only serve to optimize through iterativesearching techniques. Analytic and asymptotic expansion techniques can be used to solve thegoverning system of thermoelectric differential equations with fewer or less severe assumptionsthan the classic case. Analytic methods can provide meaningful closed form solutions and generatebetter physical understanding of the conditions for when simplifying assumptions may be valid.In obtaining the analytic solutions a set of dimensionless parameters, which characterize allthermoelectric couples, is formulated and provide the limiting cases for validating assumptions.Presentation includes optimization of both classic rectangular couples as well as practically andtheoretically interesting cylindrical couples using optimization parameters physically meaningful toa cylindrical couple. Solutions incorporate the physical behavior for i) thermal resistance of hot andcold shoes, ii) variable material properties with temperature, and iii) lateral heat transfer through legsides.

Thermoelectric Generators