Temperature Distributions During the Flash Sintering of 8% Yttria-Stabilized Zirconia Joao Gustavo Pereira da Silva": Jean-Marie Lebrun”; Hazim Ali Al-Qureshi*; Rolf Janssen*; Rishi Raj Technische Universitat Hamburg-Harburg, Institute Advanced Ceramics, D-20173 Hamburg, Germany University of Colorado at Boulder, Department of Mechanical Engineering, 80309-0427 Boulder /CO, USA © Universidade Federal de Santa Catarina, Departamento de Engenharia da Mobilidade, 89218-000 Joinville/SC, Brazil Abstract Flash sintering is a nonlinear phenomenon characterized by a sharp increase of the conductivity of the sample and concomitant rapid densification under an electric field in low temperatures in a matter of seconds, Since i is a transient phenomenon, the power dissipation on the sample is not uniform during the process. Thus, a transiont analysis is noeded to estimate the temperature of the sample during flash sintering die to Joule heating, In this work, the Finite Element Method on a coupled electro-thermal non-linear analysis was used in order to obtain the specimen temperature of SYSZ alter 5 seconds of flashing. ‘The results agree with the experimental data abtained by the flashing of dense samples and with previous literature. 1 Introduction Flash sintering is a recent processing method [?, 2, 2, 2, 2, 2, 2, 2, 2] im which dense ceramics ean be obtained at low temperatures and short sintering times. The process is characterized by a sudden increase in the sintering rate behaviors: at a certain combination of temperature and electrical field above a threshold temperature, a synchronous sharp increase of the conductivity of the ceramic is observed. The phenomenon is already confirmed for several ceramics as yttria stabilized zirconia [?, 2], magnesia doped ahunina [?], strontium titanate [2], cobalt manganese oxide (2], titania (2), yttria [2], Zirconium Boride [2] and silicon carbide [2 Several authors have already discussed possible explanations for the process. Most of the first explanations are related to a sintering process activated via Joule heating [2] or local melting at the grain boundaries [2], but recent results and discussions have led to conclusions indicating that the temperatures obtained uring flash sintering maybe are not high enough to explain thereby the densification behavior [2, 2, 2]. New mechanisms, such as the nucleation of defects embryo under the effect of polarization by the field, have been proposed to account for both, the higher conductivity and self-diffusion (sintering) observed [2 ‘This work addresses the sample temperature during flash sintering via the finite-element method (FEM). In the literature, there is already an example of FEM calculations on flash sintering of 3% mol yttria-doped zirconia [2], but the prescribed boundary conditions were simplified (constant power dissipation assumed) in order to solve the problem. This present work concerns using the prescribed voltage as a boundary condition taking into account the contact resistance, and then calculating the current flow and related Joule heating dissipation power on the sample geometry, using these data as an input for the temperature calculations in ‘ transient regime. In addition to the simulation, the transient temperatures are measured experimentally, ‘and compared to different methods of indirect estimation of temperature2 Experimental and Simulation Method 2.1 Experimental ‘The samples were fabricated with a mixture of the base SYSZ powder (Tosoh 8Y-E, Japan) with 5 wt% binder (PVA) and distilled water, mixed on a ball mill for at least four hours. ‘The mixture was then dried im an oven at 90°C, and ground again to powder in a mortar and pestle. 1 g of the powder was uniaxially pressed in a dog-bone shaped die to a relative green density of 52-55%. The binder removal was carried out ‘an oven for at least 1.5 hours at 600°C. The samples were sintered using a heating rate of 10°C per minute until 1350°C and then maintained for a further two hours, in order to get fairly dense samples (99% TD). ‘The gauge length dimensions are 16 x 2.9 x 1.8 mm giving a cross section of 5.22 mm®, After sintering, the contacts were filled with platinum paste, and the specimen is fitted on the four-point probe. Four point probe measurements associated with pyrometer temperature during flashing of dense 8% yttria doped zirconia specimens were done in order to estimate the conductivity behavior and generate data for the sitmulations. The experimental set up consists of a dog-bone shaped specimen with four holes, in which the outermost ones are connected to the power source (Sorensen 3000-2, Sorensen, San Diego, CA) and the inner ones are connected to a voltmeter (Keithley 2000, Keithley Instruments, Cleveland, OH), in order to estimate the contact resistance of the sample during the flash process. ‘The probe has a thermocouple and is placed on the hot zone of a furnace. The specimen temperature was measured with a pyrometer focused on the sample gauge assuming a specimen emissivity of 0.9 and later corrected to 0.7 [2] in the data treatment (CTLM-1, Micro-Epsilon, Messtechnik GmbH & Co, Ortenburg, Germany), ‘The flash experiments were conducted at a constant furnace set temperature of 850°C (thermocouple temperature = 863°C). After waiting at least fifteen minutes for the sample to reach the furnace temperature, an electric field of 166 Vem~1 (300 V between the outer holes) was applied as a step function. The sample ‘was kept 30 seconds under the electrical field followed by another 30 seconds of electrical field turned off, allowing the sample to cool down and return to a normal conductivity state before applying the new step fumetion. 2.2 Simulation Method ‘The finite element analysis was conducted on a commercial software (Ansys Workbench 16.0) using firstly an clectrical analysis to determine the magnitude of the electrical fields on the sample, based on the meastured resistivity of the sample during the flash state on the experiments. Densification is not taken into account by this model. The FEM simulation tries to follow the same pattern of heating, cooling and re-heating as described on the experimental section. ‘The electrical analysis uses the Maxwell's equations for continuity [Pl ‘V(-eVe) =0 () B=-Vo (2) =ob (3) where o is the electrical conductivity, 6 is the electric scalar potential, F is the electrical field vector and J is the current density vector. ‘The transient heat transfer equation was used to calculate the temperature field on the sample. The general equation for transient heat transfer with heat generation is [2] [ree av = [ viove) av [atv [ldcicon inte ) where », Cp, 6, t, V, k, and S are respectively, the density, specific heat, temperature, time, volume, thermal conductivity. The terms ge, dcono-4d: de tefer to the heat flux terms on the various surfaces, which respectively account for heat dissipation by, conduction, convection and radiation and q. is the internal heat generation, Which in this model refers to the heat generation related to Joule heating, Internal heat generation by Joule heating is given by [2] —Vo)o(—Vo) (8)‘Table 1: Material Properties 8YSZ Density (g/cm) 5.68 21.45 ‘Thermal Conductivity (W/em°C) 1.7 x 10-2 08 Specific Heat (erg/g°C) 502% 10" 1.3.x 10° Resistivity (Ohm em) Adjustable 1.05 x 10-> ‘The mesh was automatically generated with quadrangular elements, and seeded in order to have at least at the thickness direction, ‘The mode itself consists of the 8YSZ dogbone and the holes filled in order to represent the wires and the platinum paste contact. The power dissipation on the contacts is adjusted with the experimental data results, in a figure of 4.7 Q/em? ‘Table 1 summarizes the properties of the materials used for this simulation. The 8YSZ conductivity on the flashing state is taken from the experiments, since it shows a behavior different from the reported data. Similar electronic bekavior of zirconia in high temperatures is reported in [2 ‘The boundary conditions of the model are the following: For the electrical model, one of the outer holes is prescribed with a 300V potential and the other one at OV. In the thermal model, the heat losses by convection (stagnant air) and radiation are taken into account in a furnace temperature of 850°C. ‘This ‘model does not take into account the radiation heat transfer from the furnace to the sample. 3 Results and Discussion 3.1. Flash state conductivity measurements Fig. 1 is the electrical field response in the flash state, At a furnace set temperature of 850°C (thermocouple temperature = 863°C), a difference of potential of 300 V (166 Vem™1) is applied on the sample, which undergoes flashing and the voltage control switches rapidly to current control, It ean be seen that the power dissipation on the contact between wire and sample (Which ean be inferred from the difference between the field on the outer and inner electrodes) is a relevant factor to be considered, and one of the advantages of the four-point method. Two distinct regions can be observed: one shortly after the power surge, where the resistivity of the sample decreases, and one quasi steady-state, where the resistivity reaches a constant level. Figure 2 summarizes the outer sample surface temperature response of the sample during the flash process, as measured by the pyrometer. It follows roughly the same behavior of the electrical field, with also two distinet regions: the transient part where the temperature increases and reaches a quasi-steady state as soon the electrical field is constant in the experimnent, followed by a sharp decrease when the electrical field is removed. The increase in temperature and respective stabilization being synchronous with the electrical field is a strong indicator that Joule heating is the main mechanism on temperature increase. ‘The resistivity during the flash state was calculated in the two different regimes: the steady state resistiv- ity (Fig 3a.) was calculated from the average values of pyrometer temperature and current / electrical field in the steady state for the different current densities, and the transient resistivity (Fig. 3b) was calculated from each pulse response of pyrometer temperature, electrical field and current corresponding to different current densities. The values were fitted on the following equation to yield the activation energy for each regime: Ae p= emt (6) _& o nor = thn, a} ‘The linear regression in the quasi-steady state yields an activation energy of 0.56 eV, which is much lower from the expected ionic conduction in 8YSZ. This may be explained by the higher mobility of earriers on the flash-sintered state, related to the mobility caused by the generation and recombination of Frenkel defects‘The resistivity activation energy as a fiction of temperature in the transient part of the experiments was found to be 0.87 eV, in agreement with the expected literature value, pethaps evidencing two different carrier mobilities during the experiment. Of important notice is to consider the nature of the transient measurements. ‘The response time of the pytometer used on this set of experiments is around 120 ms, and is near to the same order of magnitude as the process itself. Even though, the data obtained fits the resistivity model from equation 6 and is on ‘agreement with the reported literature values. 3.2. FEM Model Figure 4 shows the calculated current density. In the present conditions, it equals an average current of 0.38 (~5.7A/em2). It ean be seen that even with the limitations imposed by the inner holes, the current itis still fairly constant and unidirectional in the specimen gauge length. Figure 5 shows the temperature field after 5 seconds of flashing, already at the quasi-steady state. ‘The value calculated as maximum temperature on the surface (1015°C) is in agreement with the py- rometer (approx. 100°C) during the pulse experiments. Differences can possibly be caused by interference of the furnace walls radiation on the pyrometer measurements. ‘The internal temperatures however, seem way higher than previous estimates and could be the responsible for the violent densification, since earlier caleulations based on the extrapolation from conventional sintering [?} indicate that a temperature of ap- proximately 1900°C will be necessary to densify 3YSZ in a matter of seconds. 8YSZ follows almost the same sintering behavior, and therefore sample heating can reach the desirable sintering temperature, Other interesting result is the predicted high thermal gradient between the sample surface and interior. ‘This result can lead to a high densification gradient and is indeed observed in some experiments, specially in high current limits. 3.3 Different temperature estimates and the influence on the activation energy calculation Estimating or measuring the actual temperatures during flash sintering is of vital importance to determine the main mechanisms of the process, as well to explain the non-linear behavior of the material conductivity and transport processes along the process. Due to the high heating rates of the process, simple measurements stich as using a thermocouple near to the sample can yield unnaccurate results. Figure 6 compares the activation energy calculation using the measured as well the calculated tempera- tures, the actual temperatures measured with the pyrometer are compared with the steady state temperatures from the FEM simulations and also with an estimate of temperature based on the black body radiation model Tr _f,, woo. (vy) x haeG)] 7 ‘Which in turn, ean either include the dissipated power due to the contacts, taking into account the whole dc power supplied to the sample, or only the dissipated power due to the electrical field on the sample during flashing, ‘Those different methods highly influence the calculation of the activation energy. As in case of the actual measurement, an activation energy of 0.56 eV is in accord to the FEM calculations (0.59 eV). ‘The black body estimates yield values of 0.72 and 0.86 eV for the cases with and without contact resistance included, respectively. Care should be taken when drawing conclusions from measurements based on temperature estimates, since it can lead to an underestimation of the activation energy for electronic or ionic transport oon the flashing ceramic. 4 Conclusions ‘The temperature field and the surge on temperature caused by Joule heating during flash sintering were caleulated for the boundary conditions used. ‘The values for outer temperature agreed with the pyrometermeasurements made during flashing of dense 8YSZ samples. ‘The different carrier mobilities on the transient and semi-quasi state are indicators of different electronic behaviors during flash sintering, most probably related to the generation and occupation of defects on the materials structure. ‘The generation of these defects could be related to the strange sintering behavior observed during flash sintering, ‘Temperature measurement during flash sintering can lead to different conclusions on the activation en- cergies depending on the measurement or estimative method. Careful measurements and awareness of the limitations of the estimative methods should be taken into account when drawing conclusions about the mechanisms of electronic transport during flash sintering 5 Acknowledgements ‘The authors would like to thank CNPq (Project 246267/2012-7, Ciencia sem Fronteiras) and DAAD for the financial support for this project. We gratefully acknowledge financial support from the German Research Foundation (DFG) via SFB 986 "M3", project C5. ‘The experiments reported in this article and Rishi Raj were supported by the Basic Energy Seiences Division of the Department of Energy under Grant No: DE- F.G02-07ER46403. Jean-Marie Lebrun was supported by the Office of Naval Research under the direction of Dr. Lawrence Kabacoff under grant munber NOOOLM-12-1-0710 References [1] Cologna M, Rashkova B, Raj R. Flash sintering of nanograin zirconia in j5s at 850C. J As [93] 35569 (2010) [2] Cologna M, Prette, ALG, Raj R. 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