Gd2Zr2O7 Research Articles

Promoting transparency: Defect-driven sintering of Gd2Zr2O7 ceramics for advanced radiation applications

Transparent Gd2Zr2O7 (GZO) ceramics show significant potential for radiation detection and nuclear energy applications. However, scalable production through cost-effective solid-state vacuum sintering is challenging due to the material's high melting point and low thermal conductivity. This study introduces a novel approach by incorporating excess Gd to increase lattice defects, such as cation disorder and oxygen vacancies, which have low formation energy. This strategy lowers the energy barrier for ion diffusion, enhances material migration during sintering, and promotes the elimination of residual pores, leading to high densification. We examined the densification behavior of GZO compositions with varying Gd content (Gd1.8Zr2O6.7 to Gd2.5Zr2O7.75) during vacuum sintering at 1450°C to 1900°C, focusing on phase transformation, grain growth, and pore elimination. Notably, the optimal sample achieved 78.3 % transmittance, approaching the theoretical maximum. These findings offer a promising route for the large-scale production and commercialization of transparent GZO ceramics for advanced radiation applications.

Preparation of spherical Gd2Zr2O7 powders by RF induction thermal plasma process

Spherical Gd2Zr2O7 (GZO) powders with a uniform particle size distribution are successfully prepared using a novel industrial approach, which combines spray-drying process and thermal plasma sintering technology together. In this, GZO powders with pyrochlore structure as the main phase are first synthesized via a solid-state reactive route using a mixture of the milled Gd2O3 powders and ZrO2 powders as starting materials. The influence of sintering temperature on the microstructure of prepared powders is researched. Then, GZO granules are prepared after wet-grinding and spray-drying process, which exhibit a spherical shape with the average particle size of 46.5 μm. RF induction thermal plasma is finally used to sinter the granulated particles, and the influence of feeding rate on the properties of spherical powders is investigated. The apparent density of plasma sintered GZO spherical powders is increased from 1.53 g/cm3 to 2.29 g/cm3 when the feeding rate of granulated powders is 80 g/min, and further increased up to 3.90 g/cm3 when the feeding rate is 15 g/min. Such powders are in potential demand for plasma sprayed coatings and additive manufacturing techniques, and the successful synthesis of spherical GZO powders may guide the way toward the preparation of many other spherical rare earth zirconates powders.

Influence of electrodes on the resistive switching characteristics of Al/Gd2Zr2O7/E (E=Al or ITO) RRAM devices

Sol-gel derived amorphous Gd2Zr2O7 (GZO) thin films with Al/GZO/E (E = ITO or Al) structures were prepared to demonstrate the effect of electrode material on the switching behavior of resistive random access memory (RRAM) devices. All devices exhibit bipolar resistive switching (BRS) mode. After the post-metal annealing (PMA) treatment, the AlOx interfacial layer contributes to enhancing oxygen ion storage capacity and limiting the electromigration of aluminum metal. The forming-free Al/GZO/ITO device exhibits a switching cycle of 3027, a Vset/Vreset ratio of −1.83 V/0.56 V, a Ron/Roff ratio of approximately 10, and a retention time of 104 s. And the Al/GZO/Al device features a dual-layer AlOx structure, significantly improving the integrity of filament rupture to reduce leakage current and increase the switching window. Its switching cycle is 1946, with a Vset/Vreset ratio of −3.47 V/0.29 V, a Ron/Roff ratio of approximately 102, and a retention time of 104 s. The oxygen storage capacity of the dual-layer AlOx interfacial layer in the Al/GZO/Al device surpasses that of the Al/GZO/ITO device, allowing for a reduction in the reset voltage and ensuring more complete filament rupture, thereby enhancing the RHRS. Accordingly, GZO thin films can be applied to achieve the desired RS characteristics on different electrodes, making them promising candidates for RRAM applications.

Densification mechanisms during high-pressure sintering of nanocrystalline Gd2Zr2O7 ceramic

High-pressure sintering (HPS) is a promising technique for producing nanocrystalline ceramics with unique properties. However, the densification mechanisms of HPS for nanocrystalline ceramics at different sintering stages remain controversial. This study focuses on Gd2Zr2O7 (GZO) nanocrystalline ceramics, investigating their microstructure evolution and densification behavior under varying pressures, temperatures, and dwelling times. The HPS process involves distinct stages: cold compaction, hot compaction, and isothermal progression. During cold compaction, densification is driven by the breakdown of aggregates, particle rearrangement, and local plastic deformation, resulting in a relative density of 84.8 %. The intermediate stage achieves an increase to ∼93.7 % in relative density by grain boundary-mediated plastic deformation mechanism. The final isothermal stage, held at 500 °C/5 GPa, achieves nearly full density (∼99.2 %) through diffusion creep, eliminating microstructural defects. This comprehensive understanding of HPS densification mechanisms, exemplified by GZO ceramics, contributes to advancing nanocrystalline ceramic applications.

High-capacity isomorphic immobilization and leaching mechanism of Gd2Zr2O7-based ceramic waste form

Gd2Zr2O7(GZO)-based ceramic waste form has attracted broad interest due to its potential applications in the long-term disposal of high-level nuclear waste. However, its high-capacity isomorphic immobilization and leaching mechanism are not well understood yet. Herein, GZO-based waste form with a single pyrochlore phase and homogeneous element distribution, achieving an isomorphic waste load as high as 50 wt%, was fabricated successfully. Isomorphism failure of the waste form is due to the Ln6MoO12 (Ln is lanthanides) formation and direct precipitation of PdO from the oversaturated solid solution. Chemical durability tests showed that the 42-day leaching rates of nearly all elements in the waste form with the maximum waste load were only between 10−6 and 10−5 gm−2d−1. The leaching of 0.5SW·0.5GZO over a period of 42 days is primarily controlled by dissolution, leading to a gradual restructuring of the surface in two distinct stages: the formation of an amorphous passivation film and the agglomeration of amorphous precipitates. Notably, the formation of the amorphous passivation film stands as the primary factor influencing the leaching rate of the waste form.

Effects of Gd3+ substitution on the structure, photoluminescence, scintillation, and thermometric features of Pr3+:Lu2Zr2O7 phosphors

AbstractIn this study, it is shown how the photoluminescence, scintillation, and optical thermometric properties are managed via the introduction of Gd3+ ions into Pr3+:Lu2Zr2O7. Raman spectra validate that partial replacement of Lu3+ with Gd3+ can promote the phase transition of Lu2Zr2O7 host from the defective fluorite structure to the ordered pyrochlore one. Upon 289 nm excitation, all the samples emit the 483 (3P0 → 3H4), 581 (1D2 → 3H4), 611 (3P0 → 3H6), 636 (3P0 → 3F2), and 714 nm (3P0 → 3F4) emissions from Pr3+ ions, which are enhanced with the addition of Gd3+ ions due to the modification of crystal structure. Dissimilarly, the X‐ray excited luminescence spectra consist of a strong emission located at 314 nm from Gd3+ ions (6P7/2 → 8S7/2), together with the typical emissions from Pr3+ ions, which exhibit different dependences on the Gd3+ concentration. When the luminescence intensity ratio between the 3P0 → 3H6 (611 nm) and 1D2 → 3H4 (581 nm) transitions is selected for temperature sensing, Pr3+:(Lu0.75Gd0.25)2Zr2O7 shows the optimal relative sensing sensitivity of 0.78% K−1 at 303 K, which is higher than that of the Gd3+‐free sample. Therefore, the developed Pr3+:(Lu, Gd)2Zr2O7 phosphors have the applicative potential for optical thermometry, X‐ray detection, and photodynamic therapy.

Immobilization and He+ irradiation effects of Gd2Zr2O7-based ceramic waste form for radioactive waste disposal

The Gd2Zr2O7(GZO)-based ceramic waste form exhibits promising potential for radioactive waste immobilization. However, the isomorphic immobilization capacity and irradiation effects of GZO-based ceramic waste forms with varying waste loads remain inadequately understood. This study employed a facile combustion method to synthesize ceramic powders and utilized conventional sintering with a relatively short dwelling time to fabricate GZO-based ceramic waste forms. We investigated the isomorphic immobilization behavior and He ion irradiation effects of the synthesized waste forms. The outcomes demonstrate that GZO effectively immobilizes simulated waste composed of 11 types of oxides, achieving a waste load as high as 50 wt% with a single pyrochlore phase and homogeneous element distribution. Under He+ irradiation, aggravated structural degradations, including exacerbated lattice swelling, increased amorphization degree, and premature He bubble chain/microcrack formation, were observed in GZO-based waste forms with an increasing waste load.

Thermo-physical properties, morphology and thermal shock behavior of EB-PVD thermal barrier coating with DLC YbGdZrO/YSZ system

(Yb0.1Gd0.9)2Zr2O7 (YbGdZrO) rare earth modified zirconate ceramics is one of the novel thermal barrier coatings (TBCs) materials which has attracted much attention in recent years and is suitable for higher temperature applications. YbGdZrO ceramic powders gained from solid-phase synthesis show a single defect fluorite structure. After calcined at 1723 K upon 400 h, whose powder does not form any new phases and exhibit outstanding thermal durability. The thermal expansion coefficient of YbGdZrO ceramics with the elevated temperature to 1573 K is attained to 10.76 × 10−6 K−1, which is slightly smaller than that of Gd2Zr2O7 (GZO) material (10.98 ×10−6 K−1) at the same temperature. The arithmetic mean of coefficient of thermal diffusion of YbGdZrO bulks measured at 1273 K is 0.385 mm2/s, that seems to be equivalent to that of GZO ceramics (0.388 mm2/s, 1273 K). The X-ray diffraction feature peaks of electron beam physical vapor deposition (EB-PVD) YbGdZrO ceramic coatings almost resemble to its ingot, except that the crystal face indices of their two strongest peaks are different. The pyramid-like shape can be scrutinized on top tip of columnar grain of the as-deposited YbGdZrO ceramic layer, which is associated to the cubic lattice in the fluorite structure. After 3000 cycles of flame thermal shock, the upper half of the coated sample surface occurs light green. While the closer is the position to edge of the specimen, the more obvious is the color. In addition, many small black spots with disorderly distribution are observed on the coating surface. A large number of irregularly distributed and cross-linked micro-cracks are displayed on the surface of YbGdZrO ceramic top layer as well as the averaged width of these micro-cracks is determined to be ∼8.523 µm. Although the ceramic coating appears to have a small number of layered exfoliation, the chemical composition of the exposed region still contains only elements of Yb, Gd, Zr and O. It does not stretch to either interface of double-ceramic-layer (DCL) YbGdZrO/YSZ or interior of YSZ ceramic coating.

Near-Infrared Trapping by Surface Plasmons in Randomized Platinum-Ceramic Metamaterial for Thermal Barrier Coatings.

As the operation temperature of next generation gas turbine is targeted to be 1800°C toward a higher efficiency and lower carbon emission, the near-infrared (NIR) thermal radiation becomes a major concern for the durability of the metallic turbine blades. Although thermal barrier coatings (TBCs) are applied to provide thermal insulations, they are translucent to the NIR radiation. It is a major challenge for TBCs to achieve optically thick with limited physical thickness (usually < 1mm) for effectively shielding the NIR radiation damage. Here, an NIR metamaterial is reported, where a Gd2 Zr2 O7 ceramic matrix is randomly dispersed with microscale Pt (0.53 vol%) nanoparticles with a size of 100-500nm. Attenuated by the Gd2 Zr2 O7 matrix, a broadband NIR extinction is achieved through the red-shifted plasmon resonance frequencies and higher-order multipole resonances of the Pt nanoparticles. A very high absorption coefficient of ≈3 × 104 m-1 , approaching the Rosseland diffusion limit for a typical coating thickness, minimizes the radiative thermal conductivity to ≈10-2 W m-1 K-1 and successfully shields the radiative heat transfer. This work suggests that constructing a conductor/ceramic metamaterial with tunable plasmonics could be a strategy to shield NIR thermal radiation for high temperature applications.

Oxidation Behavior of Single-Layer Gd2Zr2O7, and Gd2Zr2O7/YbSZ, and Double-Layer YSZ + Gd2Zr2O7/YbSZ Thermal Barrier Coatings

Oxidation is one of the failure mechanisms of gas turbines under operating temperature. Yttria-stabilized zirconia (YSZ) is well-known ceramic topcoat material of thermal barrier coatings (TBCs), but it has some drawbacks. From this point of view, other new materials such as rare earth zirconate are interesting. In the present research, single-layer Gd2Zr2O7 (GZO), and GZO/YbSZ (Gd2Zr2O7 + 50 wt% YbSZ), and double-layer YSZ + GZO/YbSZ (YSZ/Gd2Zr2O7 + 50 wt% YbSZ) topcoats as TBC were deposited by air plasma spraying. To estimate the phase stability of homogeneous mixtures of GZO (pyrochlore) and YbSZ (tetragonal), heat treatment was conducted at 1400 °C and showed complete conversion to a single-cubic (fluorite) phase after 100 h. The as-sprayed TBCs were subjected to oxidation for different times at 900 °C, and their features were investigated by different analysis techniques (SEM and XRD). The microstructural analysis indicated that the thickness of the thermally grown oxide layer was less for GZO coating due to reduced oxygen diffusion. Conversely, because of the lower fracture toughness and lower thermal expansion of GZO, it had a considerably less lifetime. It was concluded that coatings with the new composition GZO/YbSZ exhibited higher oxidation resistance and longer lifetime than GZO coatings.

Role of structural ordering on the radiation response of Gd2Zr2O7 pyrochlore

Complex oxides with pyrochlore and fluorite phases offer several advantages for the Immobilization of actinides or high-level radioactive wastes. In this report, we present the different behavior of structural ordering/crystallinity of Gd2Zr2O7 (GZO) ceramics upon sintering at two different temperatures (1400°C–1500 °C). XRD and Raman spectroscopy studies revealed the enhancement of structural ordering/crystallinity with the increase of sintering temperature. Further, the ion irradiation experiments using 100 MeV iodine at the fluence of 1.0 × 1014 ions/cm2 were performed to investigate the radiation effects on both GZO ceramics. The irradiation studies insinuate that the GZO ceramic sintered at 1500 °C possesses relatively better radiation resistance than GZO ceramic sintered at 1400 °C. The variation in the radiation resistance response of GZO ceramics seems associated with the different degrees of structural ordering. These results suggest the role of structural ordering in the radiation resistance response of GZO ceramics. The relatively better radiation tolerance of GZO15 ceramic with some extant pyrochlore phase ordering may be suitable for applications in harsh environments.

Reaction mechanisms of Gd2Zr2O7 in silicate melts derived from CAS

Infiltration mechanisms at high temperatures of sand & ashes (CAS) in aircraft thermal barrier coatings (TBC) have been widely studied using the pyrochlore phase Gd2Zr2O7 (GZ) as TBC. Novelty of this study is GZ reactivity with each or a mix of oxides derived from CMAS have been scrutinized in order to better assess the diffusion, stability and role of each reactivity products in mitigation mechanisms across the CAS-GZ system. In particular, Gd+III, Si+IV, O-II diffusion mechanisms at the GZ/SiO2 interface have been discussed. These mechanisms shed light on why Gd-oxyapatites are the predominant phases at interfaces between silica-rich medium such as CAS and GZ when reactions are not complete, in contrast to thermodynamic data. Moreover, Gd2Si2O7 phases are closely linked to the growth of Gd-oxyapatites and are the seat of the diffusion barrier to Si+IV species, which further explains why GZ coatings shortly stops CMAS infiltration.

Investigation of vermiculite infiltration effect on microstructural properties of thermal barrier coatings (TBCs) produced by electron beam physical vapor deposition method (EB-PVD)

Thermal barrier coatings (TBCs) are protective coating systems that are mostly utilized to improve the thermal insulation and functional performance of gas turbine engines and other aircraft components that are both stable and movable. These coatings protect materials operating in harsh conditions from structural damage caused by corrosion, oxidation, the CaO-MgO-Al2O3-SiO2 effect (CMAS), thermal shock, volcanic ash, and vermiculite deposits at high temperatures. In this study, CoNiCrAIY metallic bond coatings were coated on Inconel 718 super alloy using a high velocity oxygen-fuel (HVOF) deposition technique. Then, single YSZ, Gd2Zr2O7 (GZ), and double YSZ/GZ based ceramic topcoats were applied to the bond coats by using the electron beam physical vapor deposition (EB-PVD) method. The produced TBC samples and the uncoated Inconel 718 superalloy substrate were subjected to vermiculite (VM) deposition at 1250 °C for 4 h, and then the coatings were characterized. To determine the phase structures, microstructural and mechanical properties of the TBCs, X-ray diffractometer (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer elemental mapping analysis (EDS), stereo microscopy analyses, porosity, and hardness measurements were used. The obtained results were comparatively evaluated with the recent related studies in the literature.

Suppressing disorder-order phase transition of Gd2Zr2O7 pyrochlore by Dy3+ doping and their impact on luminescence

The functionality of the Gd2Zr2O7 matrix is dictated by ordering at the cationic lattice (pyrochlore or defective fluorite) and associated local manifestations. In this work, we have synthesized nano and bulk undoped Gd2Zr2O7 (GZO) and Gd2Zr2O7:Dy3+ (GZOD) by molten salt synthesis adopting a crystal engineering approach and investigated their impact on photoluminescence properties. DFT calculations along with the higher intensity of yellow emission in the bulk GZOD confirm that the presence of Dy3+ is energetically favorable in defect fluorite structure compared to ordered pyrochlore counterpart. Increase/adjustments in the Zr–O bond distances in Dy3+ surroundings facilitate the release of local strain/stress in defective fluorite structure, which is not feasible in the perfectly ordered pyrochlore structure. Overall, the preference of defective fluorite structure by the GZO NCs, GZOD NCs, and bulk GZOD has been attributed to inherent flexibility in local structure with varying coordination numbers and polyhedral arrangements that assist in reducing the strain arising due to smaller particle size and/or by Dy3+ doping. It is believed that the present work provides simplistic pathways to control the order-disorder transformation, and in turn, the functionality of the Gd2Zr2O7 matrix for better hosting of nuclear waste and phosphor centers.

Grain-size dependent thermal conductivity of Gd2Zr2O7 ceramics

In this work, the grain-size dependent thermal conductivity of Gd2Zr2O7 (GZO) ceramics has been studied. The investigation show that the thermal conductivity limit of the GZO ceramic can be achieved when the grain size is reduced to ∼7.5 nm. The very low thermal conductivity can be related to the high volume fraction of grain boundary/triple junction phases (GB/TJ) in nanocrystalline GZO ceramic, which is comparable to that of the grain phase. This result demonstrates that reducing grain size is a valid strategy to decrease the thermal conductivity in polycrystalline materials. Significantly, this grain-size dependent thermal conductivity can be described by a simple composite model, which treated the nanocrystalline GZO ceramic as a two-phase mixture model consisting of grain phase and GB/TJ phase.

Enhanced calcium–magnesium–aluminosilicate (CMAS) resistance of GdAlO3 (GAP) for composite thermal barrier coatings

AbstractThe impact of calcium–magnesium–alumino‐silicate (CMAS) degradation is a critical factor for development of new thermal and environmental barrier coatings. Several methods of preventing damage have been explored in the literature, with formation of an infiltration inhibiting reaction layer generally given the most attention. Gd2Zr2O7 (GZO) exemplifies this reaction with the rapid precipitation of apatite when in contact with CMAS. The present study compares the CMAS behavior of GZO to an alternative thermal barrier coating (TBC) material, GdAlO3 (GAP), which possesses high temperature phase stability through its melting point as well as a significantly higher toughness compared with GZO. The UCSB laboratory CMAS (35CaO–10MgO–7Al2O3–48SiO2) was utilized to explore equilibrium behavior with 50:50 mol% TBC:CMAS ratios at 1200, 1300, and 1400°C for various times. In addition, 8 and 35 mg/cm2 CMAS surface exposures were performed at 1425°C on dense pellets of each material to evaluate the infiltration and reaction in a more dynamic test. In the equilibrium tests, it was found that GAP appears to dissolve slower than GZO while producing an equivalent or higher amount of pore blocking apatite. In addition, GAP induces the intrinsic crystallization of the CMAS into a gehlenite phase, due in part to the participation of the Al2O3 from GAP. In surface exposures, GAP experienced a substantially thinner reaction zone compared with GZO after 10 h (87 ± 10 vs. 138 ± 4 μm) and a lack of strong sensitivity to CMAS loading when tested at 35 mg/cm2 after 10 h (85 ± 13 versus 246 ± 10 μm). The smaller reaction zone, loading agnostic behavior, and intrinsic crystallization of the glass suggest this material warrants further evaluation as a potential CMAS barrier and inclusion into composite TBCs.

Synthesis of Gd2Zr2O7 Coatings Using the Novel Reactive PS-PVD Process

Ceramic topcoats of thermal barrier coatings (TBCs) make it possible to increase the working temperature of the hot sections of jet engines. Yttria-stabilized zirconia oxide (YSZ) is usually used to protect the turbine blades and vanes against high temperature and oxidation. It is necessary to develop new materials which can operate at higher temperatures in a highly oxidizing gas atmosphere. Re2Zr2O7-type pyrochlores are promising YSZ replacements. Usually, they are produced by mixing pure oxides in the calcination process at higher temperatures. In a recent article, the new concept of pyrochlore synthesis during the deposition process was presented. The new technology, called reactive plasma spray physical vapor deposition (reactive PS-PVD), was developed and a Gd2Zr2O7 (GZO) coating was achieved. The reactive PS-PVD process allowed for the use of a mixture of untreated ZrO2 and Gd2O3 powders as reactants, instead of the commercially available gadolinium zirconate powders used in other types of processes. The results of microstructure observations revealed a columnar microstructure in the produced ceramic layer. The phase composition indicated the presence of gadolinium zirconate. Thermal analysis showed a decrease in the thermal conductivity in the range of 700 to 1200 °C of the produced layers, as compared to the layer made of the currently used conventional YSZ.

Phase relations and thermomechanical properties of (Gd2Zr2O7)1\u2212x(YbSZ)x based thermal barrier coatings (0\u2009\u2264\u2009x\u2009\u2264\u20090.98)

Doped Gd2Zr2O7 materials have interesting properties as thermal barrier coatings (TBC) to replace the YSZ topcoats traditionally used. Here we investigate the thermomechanical properties and phase relations of Gd2Zr2O7 (GZO) alloyed with 5 mol% Yb2O3 stabilized ZrO2 (YbSZ) in the composition range (Gd2Zr2O7)1−x(YbSZ)x, 0 ≤ x ≤ 0.98. With increasing YbSZ content, phase transformations from ordered to disordered pyrochlore to fluorite and tetragonal structures were observed. The thermal expansion coefficient (TEC) and Vickers hardness were correlated showing a maximum hardness (~ 11.5 GPa) and minimum TEC at x = 0.82. At 1000 °C, the TEC for the end members, x = 0 and 0.98, were 11.4 and 11.3 × 10–6 K−1, respectively. The fracture toughness, KIC, showed an average value around 1.5 MPa m0.5 for x ≤ 0.93 and increased significantly at x = 0.98 reaching 5.4 MPa m0.5 due to the presence of a ferroelastic phase. For TBC applications, compounds with x = 0.98 show promise due to high TEC and high KIC.Graphic abstractFig. 5a summarize the most important results in the manuscript. Showing a significant increase in fracture toughness for compositions with x=0.98.

Hot corrosion of Gd2Zr2O7, Gd2Zr2O7/YbSZ, YSZ + Gd2Zr2O7/YbSZ, and YSZ thermal barrier coatings exposed to Na2SO4 + V2O5

Gd2Zr2O7 ceramic is considered as a potential candidate for thermal barrier coatings. Here we present hot corrosion behavior of single layer Gd2Zr2O7 (GZO), Gd2Zr2O7 + 50 wt% YbSZ (GZO/YbSZ), YSZ and double-layer YSZ/Gd2Zr2O7 + 50 wt% YbSZ (YSZ + GZO/YbSZ) coatings prepared by air plasma spraying on Inconel 625 substrates. Prior to hot corrosion the fracture toughness of the coatings was assessed by Vickers indentation showing a variation between 0.6 and 2.3 MPa.m1/2 where the GZO/YbSZ coating exhibited the highest fracture toughness. The hot corrosion test was conducted by exposing the coatings to an equimolar mixture of Na2SO4 and V2O5 at 750 °C. After the hot corrosion test, the type of phases, chemical composition, microstructure and crack formation were investigated. Formation of GdVO4 and YVO4 was observed as the corrosion products in the GZO containing coatings and the YSZ coating, respectively. All coatings showed the formation of monoclinic zirconia after the corrosion test. The Gd2Zr2O7 + 50 wt% YbSZ (GZO/YbSZ) coating showed the best hot corrosion resistance due to reduced reactivity and enhanced fracture toughness and represents a new composition with properties promising for TBC applications.

Polysulfone-Gd2Zr2O7 mixed-matrix membranes with superior radiation resistant properties: Fabrication and application of a membrane device for radioactive effluent treatment

This is the first study undertaken towards development of mixed-matrix membranes (MMMs) with enhanced radiation resistant attributes by reinforcement of nanostructured Gd2Zr2O7 (GZO) within polysulfone (Psf) host-matrix. The study describes synthesis and characterization of GZO in disordered, defect-fluorite structure, having average crystallite size of 31(±3) nm. Membranes prepared with different loading of GZO (up to 2 w/w% of Psf) are exposed to γ-radiation up to a dose of 1000 kGy in aqueous environment. The effect of radiation on the structural, mechanical, and thermo-oxidative properties of MMMs has been compared with that of radiation-sensitive Psf membrane. The ultrafiltration performance of the (un)irradiated Psf and MMMs reveal that an optimum reinforcement of GZO at 1 (w/wPsf)% offers ~10 times radiation resistant MMM, compared to that of Psf membrane. The MMM with 1 (w/wPsf)% GZO was rolled into 2512 spiral configuration and a highly-compact device was developed for treatment of radioactive effluent. Based on the flux decline behaviour over 18 months duration, the fouling behaviour of the MMM module was modelled. The life-span of the MMM was predicted based on the absorbed radiation dose, GZO leaching study, and fouling behaviour. It is proposed that GZO mitigates a fraction of the impinged γ-energy in swapping of the Gd3+ and Zr4+ sites, which protects the polymeric host-matrix in-situ from radiation induced degradation. The abundance of Gd3+ and Zr4+ associated with polar O2− over the impregnated GZO further stabilizes MMMs through scavenging of the oxidizing and reducing radiolysed products of water. Thus, we report a smart approach to develop novel MMM with greater life-expectancy against high-energy radiation and further fabricate a membrane-based device for management of liquid radioactive waste.