Realizing Outstanding Energy Storage Performance in KBT-Based Lead-Free Ceramics via Suppressing Space Charge Accumulation.

The great potential of K1/2Bi1/2TiO3 (KBT) for dielectric energy storage ceramics is impeded by its low dielectric breakdown strength, thereby limiting its utilization of high polarization. This study develops a novel composition, 0.83KBT-0.095Na1/2Bi1/2ZrO3-0.075 Bi0.85Nd0.15FeO3 (KNBNTF) ceramics, demonstrating outstanding energy storage performance under high electric fields up to 425 kV cm-1: a remarkable recoverable energy density of 7.03 J cm-3, and a high efficiency of 86.0%. The analysis reveals that the superior dielectric breakdown resistance arises from effective mitigation of space charge accumulation at the interface, influenced by differential dielectric and conductance behaviors between grains and grain boundaries. Electric impedance spectra confirm the significant suppression of space charge accumulation in KNBNTF, attributable to the co-introduction of Na1/2Bi1/2ZrO3 and Bi0.85Nd0.15FeO3. Phase-field simulations reveal the emergence of a trans-granular breakdown mode in KNBNTF resulting from the mitigated interfacial polarization, impeding breakdown propagation and increasing dielectric breakdown resistance. Furthermore, KNBNTF exhibits a complex local polarization and enhances the relaxor features, facilitating high field-induced polarization and establishing favorable conditions for exceptional energy storage performance. Therefore, the proposed strategy is a promising design pathway for tailoring dielectric ceramics in energy storage applications.

Reinforcement and Deacidification for a Textile Scroll Painting (AD 1881) Using the CNF and MgO Suspensions.

The scroll paintings for ancestor trees have been used to inherit the spirit of ancestor worship as a historical record of family development since the late Ming Dynasty in China. A severely degraded scroll painting of an ancestor tree (made of cotton textiles) needs intervention and conservation treatment to mitigate further deterioration. On the basis of the previously reported characterization results for the painting, in this paper, a suspension that is composed of 0.6% cellulose nanofibril (CNF) and nanosized 0.15% MgO in aqueous solvent (denoted as the CNF-MgO susairpension) was prepared. Conventional characterization methods were used to assess the properties of model samples before and after treatment with the CNF-MgO suspension, as well as before and after degradation under two sets of conditions. The results show that the treated model samples are slightly alkaline, given the deposit of alkaline particles, and demonstrate good mechanical properties before and after degradation due to the increase in fiber-to-fiber bond and mitigation of acid-catalyzed hydrolysis. In spite of the non-transparency of CNF and MgO nanoparticles, they have little impact on the optical properties of textiles, as verified by transmittance data and the determination of color changes. This suspension was then used to reinforce and restore the scroll painting in a practical conservation process. The application of CNF and MgO nanoparticles on textile objects investigated in this study would expand our understanding of the conservation of such objects, especially for those that have already become acidic and degraded.

Giant Deformation Induced Staggered-Layer Structure Promoting the Thermoelectric and Mechanical Performance in n-Type Bi2(Te, Se)3.

Bismuth telluride has long been recognized as the most promising near-room temperature thermoelectric material for commercial application; however, the thermoelectric performance for n-type Bi2(Te, Se)3-based alloys is far lagging behind that of its p-type counterpart. In this work, a giant hot deformation (GD) process is implemented in an optimized Bi2Te2.694Se0.3I0.006+3 wt%K2Bi8Se13 precursor and generates a unique staggered-layer structure. The staggered-layered structure, which is only observed in severely deformed crystals, exhibits a preferential scattering on heat-carrying phonons rather than charge-carrying electrons, thus resulting in an ultralow lattice thermal conductivity while retaining high-weight carrier mobility. Moreover, the staggered-layer structure is located adjacent to the van der Waals gap in Bi2(Te, Se)3 lattice and is able to strengthen the interaction between anion layers across the gap, leading to obviously improved compressive strength and Vickers hardness. Consequently, a high peak figure of merit ZT of ≈ 1.3 at 423 K, and an average ZT of ≈ 1.2 at 300-473 K can be achieved in GD sample. This study demonstrates that the GD process can successfully decouple the electrical and thermal transports with simultaneously enhanced mechanic performance.

Giant dielectric response and relaxation behavior of Bi3+/W6+ co-doped TiO2 ceramics.

With the rapid development of electronic information technology, dielectric ceramics are widely used in the field of passive devices such as multi-layer ceramic capacitors. In this paper, (Bi2/3W1/3)xTi1-xO2 (BWTOx) ceramics with superior dielectric properties have been prepared by using a traditional solid-state method. Remarkably, at a (Bi2/3W1/3)4+ doping level of 0.01, a (Bi2/3W1/3)0.01Ti0.99O2 ceramic achieved a giant dielectric permittivity of ∼1.5 × 104 and a low loss tangent of ∼0.07 at 1 kHz, as well as a good temperature independence, which could satisfy the operating temperature standards for X9R capacitors. The abnormal dielectric relaxation in the low temperature region can be explained by the interface polarization. Data based on the complex impedance spectroscopy and X-ray photoemission spectroscopy results indicate that the colossal permittivity of BWTOx ceramics is mainly ascribed to the internal barrier layer capacitance effect. The findings of this work could provide valuable insights for achieving large dielectric constants and good temperature stability simultaneously in BWTOx and other related electronic ceramic materials.

A Study of Pigment, Adhesive, and Firing Temperature in Pottery Figurines Excavated from the Tomb of Qibi Ming, China.

Some painted pottery figurines were excavated from the tomb of Qibi Ming of the Tang Dynasty. A series of analytical techniques were employed to understand the craftsmanship of these painted pottery figurines. The pigment, cross-section, adhesive, and firing temperature were analyzed using microscopy (OM), energy X-ray fluorescence spectrometry (EDX), micro-Raman spectroscopy, pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS), and a dilatometer (DIL). The results demonstrated that the surface of the pigment layers had degraded to different degrees. The pigment particles were litharge, gypsum, malachite, cinnabar, hematite, minium, white lead, and carbon black. The cross-sectional images show that the painted layer of figurines 10-0966 and 10-0678 included a pigment layer and a preparation layer. The preparation layer of both pigments was lead white. Animal glue was used as an adhesive. The firing temperature of the pottery figurines was likely 1080 °C. This study can provide more accurate information with regard to the composition of the raw materials utilized in the making of these artifacts and support the selection of appropriate substances for the purposes of conservation and restoration of the painted pottery figurines.

A Study on the Materials Used in the Ancient Architectural Paintings from the Qing Dynasty Tibetan Buddhist Monastery of Puren, China.

Situated in the village of Lama Temple on the eastern bank of the Wulie River in Chengde, Puren Temple stands as one of the few remaining royal temples of great importance from the Kangxi era (1662-1722 AD). This ancient edifice has greatly contributed to the advancement of our comprehension regarding the art of royal temple painting. The present study undertakes a comprehensive analysis and identification of nine samples obtained from the beams and ceiling paintings within the main hall of Puren Temple. Furthermore, a systematic examination of their mineral pigments and adhesives is conducted. The findings from polarized light microscopy (PLM), energy-type X-ray fluorescence spectrometer (ED-XRF), micro-Raman spectroscopy (m-RS), and X-ray diffractometer (XRD) analyses reveal that the pigments present in the main hall beams of Puren Temple are cinnabar, lead white, lapis lazuli, and lime green, while the pigments in the ceiling paintings consist of cinnabar, staghorn, lead white, lapis lazuli, and lime green. The use of animal glue as a binder for these pigments on both the main hall beams and ceiling paintings is confirmed via pyrolysis-gas chromatography-mass spectrometry (Py-Gc/Ms) results. These findings hold significant implications for the future restoration of Puren Temple, as they provide valuable guidance for the selection of appropriate restoration materials.

Enhancing Energy Storage Performance in Lead-Free Bismuth Sodium Niobate-Based Tungsten Bronze Ceramics through Relaxor Tuning.

A series of tungsten bronze Sr2Na0.85Bi0.05Nb5-xTaxO15 (SBNN-xTa) ferroelectric ceramics were designed and synthesized by the traditional solid-phase reaction method. The B-site engineering strategy was utilized to induce structural distortion, order-disorder distribution, and polarization modulation to enhance relaxor behavior. Through investigating the impact of B-site Ta replacement on the structure, relaxor behavior, and energy storage performance, this study has shed light on the two main factors for relaxor nature: (1) with the increase of Ta substitution, the tungsten bronze crystal distortion and expansion induced the structural change from an orthorhombic Im2a phase to Bbm2 phase at room temperature; (2) the transition from ferroelectric to relaxor behavior could be attributed to the coordinate incommensurate local superstructural modulations and the generation of nanodomain structure regions. Moreover, we benefited from the effective decrease of ceramic grains and inhibition of abnormal growth. Finally, we obtained an effective energy storage density (Wrec) ∼ 1.6 J/cm3, an efficiency (η) ∼ 80%, a current density (CD) ∼ 1384.2 A/cm2, and a power density (PD) ∼ 138.4 MW/cm3.

The origin of dielectric relaxation behavior in TiO2 based ceramics co-doped with Zn2+, W6+ ions under a N2/O2 sintering atmosphere.

Dense (Zn0.5W0.5)xTi1-xO2 (ZWTOx) ceramics were fabricated using a conventional solid state reaction method with sintering under a nitrogen atmosphere (ZWTOx-N2) and an oxygen atmosphere (ZWTOx-O2), respectively. Colossal permittivity (ε > 104) and low loss (tan δ < 0.1) were simultaneously achieved in ZWTOx-N2 ceramics, and two types of dielectric relaxation behaviors observed were interpreted to be due to interface polarization and disassociation between oxygen vacancies and trivalent titanium ions, respectively. The impedance plots suggested that the ZWTOx-N2 ceramics are electrical heterostructures composed of semiconductor and insulator grain boundaries, which proved that the CP performance of ZWTOx-N2 ceramics almost originates from the internal barrier layer capacitance (IBLC) effect. In addition, a series of anomalous dielectric behaviors such as low permittivity and low frequency dispersion were observed for ZWTOx-O2 ceramics; polarization (P)-electric field (E) hysteresis loop curves were obtained for ZWTOx-O2 ceramics, and that impedance plots have shown that the ZWTOx-O2 ceramics display higher insulation resistivity. Density functional theory (DFT) calculations illustrated that the Zn2+-W6+ ion pairs are easy to form in ZWTOx-O2 ceramics, which causes destruction of the local lattice and thus leads to abnormal dielectric behavior. This work will provide a new strategy for defect engineering in TiO2 and other CP materials.

Superior Energy Storage Properties and Optical Transparency in K0.5 Na0.5 NbO3 -Based Dielectric Ceramics via Multiple Synergistic Strategies.

Eco-friendly transparent dielectric ceramics with superior energy storage properties are highly desirable in various transparent energy-storage electronic devices, ranging from advanced transparent pulse capacitors to electro-optical multifunctional devices. However, the collaborative improvement of energy storage properties and optical transparency in KNN-based ceramics still remains challenging. To address this issue, multiple synergistic strategies are proposed, such as refining the grain size, introducing polar nanoregions, and inducing a high-symmetry phase structure. Accordingly, outstanding energy storage density (Wtotal  ≈7.5 J cm-3 , Wrec  ≈5.3 J cm-3 ) and optical transmittance (≈76% at 1600 nm, ≈62% at 780 nm) are simultaneously realized in the 0.94(K0.5 Na0.5 )NbO3 -0.06Sr0.7 La0.2 ZrO3 ceramic, together with satisfactory charge-discharge performances (discharge energy density: ≈2.7 J cm-3 , power density: ≈243 MW cm-3 , discharge rate: ≈76 ns), surpassing previously reported KNN-based transparent ceramics. Piezoresponse force microscopy and transmission electron microscopy revealed that this excellent performance can be attributed to the nanoscale domain and submicron-scale grain size. The significant improvement in the optical transparency and energy storage properties of the materials resulted in the widening of the application prospects of the materials.

All Cubic-Phase δ-TAGS Thermoelectrics Over the Entire Mid-Temperature Range.

GeTe-based pseudo-binary (GeTe)x (AgSbTe2 )100- x (TAGS-x) is recognized as a promising p-type mid-temperature thermoelectric material with outstanding thermoelectric performance; nevertheless, its intrinsic structural transition and metastable microstructure (due to Ag/Sb/Ge localization) restrict the long-time application of TAGS-x in practical thermoelectric devices. In this work, a series of non-stoichiometric (GeTe)x (Ag1- δ Sb1+ δ Te2+ δ )100- x (x = 85∼50; δ = ≈0.20-0.23), referred to as δ-TAGS-x, with all cubic phase over the entire testing temperature range (300-773 K), is synthesized. Through optimization of crystal symmetry and microstructure, a state-of-the-art ZTmax of 1.86 at 673 K and average ZTavg of 1.43 at ≈323-773 K are realized in δ-TAGS-75 (δ = 0.21), which is the highest value among all reported cubic-phase GeTe-based thermoelectric systems so far. As compared with stoichiometric TAGS-x, the remarkable thermoelectric achieved in cubic δ-TAGS-x can be attributed to the alleviation of highly (electrical and thermal) resistive grain boundary Ag8 GeTe6 phase. Moreover, δ-TAGS-x exhibits much better mechanical properties than stoichiometric TAGS-x, together with the outstanding thermoelectric performance, leading to a robust single-leg thermoelectric module with ηmax of ≈10.2% and Pmax of ≈0.191 W. The finding in this work indicates the great application potential of non-stoichiometric δ-TAGS-x in the field of mid-temperature waste heat harvesting.

Hydroxypropyltrimethyl Ammonium Chloride Chitosan Nanoparticles Coatings for Reinforcement and Concomitant Inhibition of Anionic Water-Sensitive Dyes Migration on Fragile Paper Documents.

The fragile paper is treated to improve the stability and appearance of the paper artifact, such as washing, lining, deacidification, and reinforcement. During the above treatments, paper documents inevitably make contact with water directly, leading to the appearance change, stability decrease, and migration or fading of anionic water-sensitive dyes, which are seriously harmful to information security. Herein, Hydroxypropyltrimethyl ammonium chloride chitosan (HACC) nanoparticles were employed for the reinforcement and concomitant inhibition of anionic water-sensitive dye migration on fragile paper. HACC nanoparticles were prepared through physical ball grinding method and characterized via LPSA, SEM, TEM, XRD and FTIR. To evaluate the protective potential of HACC nanoparticles coating, the chemical and mechanical properties of coated and uncoated papers were evaluated after dry heat and hygrothermal accelerated aging. Additionally, good color stability of anionic water-sensitive dyes was observed on the paper coated with HACC nanoparticles after lining technology. Finally, the interaction mechanism between the anionic water-sensitive dyes and HACC nanoparticles was analyzed using an ultraviolet spectrophotometer and FTIR. The as-proposed technique can provide technical support to improve the mechanical properties of fragile paper and enhance the anionic water-sensitive dyes stability in the aqueous phase.

Significantly Enhanced Thermoelectric Performance Achieved in CuGaTe2 through Dual-Element Permutations at Cation Sites.

CuGaTe2 has become a widely studied mid-temperature thermoelectric material due to the advantages of large element abundance, proper band gap, and intrinsically high Seebeck coefficient. However, the intrinsically high lattice thermal conductivity and low room-temperature electrical conductivity result in a merely moderate thermoelectric performance for pristine CuGaTe2. In this work, we found that Cu deficiency can significantly reduce the activation energy Ea of Cu vacancies from ∼0.17 eV for pristine CuGaTe2 to nearly zero for Cu0.97GaTe2, thus leading to dramatic improvements in hole concentration and power factor. More remarkably, element permutations (Ag/Cu and In/Ga) at both cation sites can effectively reduce the lattice thermal conductivity at the entire testing temperatures by producing intensive atomic-scale mass and strain fluctuations. Eventually, an ultrahigh peak ZTmax value of ∼1.5 at 873 K is achieved in the composition of Cu0.72Ag0.25Ga0.6In0.4Te2, while a large average ZTavg value of ∼0.7 (323-873 K) is obtained in the Cu0.67Ag0.3Ga0.6In0.4Te2 sample, both of which are significant improvements over pristine CuGaTe2.

Microscopic Imaging Technology Assisted Dynamic Monitoring and Restoration of Micron-Level Cracks in the Painted Layer of Terracotta Warriors and Horses of the Western Han Dynasty.

Cracks are one of the most common issues affecting colored pottery relics; these can be divided into macroscopic cracks, recognizable by the human eye, and micron cracks, which cannot be observed by the naked eye. The gradual development of micron cracks eventually leads to large-scale cracks and the shedding of the coating layer. The repair of such micron cracks poses a key technical difficulty in restoring painted pottery remnants from the Western Han Dynasty. We attempt to solve this problem by reporting on a method that entails the use of a water-borne fluoropolymer material as the adhesive agent, as well as ultra-depth-of-field, digital microscopic imaging technology to build an operating platform for an optical imaging monitoring system. By making simulated ceramic samples, we systematically investigated the influences of water-borne fluoropolymer on chromaticity, adhesion, contact angle, surface morphology, and thermal stability of the paint layer. The results indicate that the color of the painted layer, when treated with the water-borne fluoropolymer, did not change, and the adhesion and contact angle of the painted layer were improved. Additionally, the outcomes of the SEM analysis show that the adhesion and hydrophobicity of the painted layer were improved because the water-borne fluoropolymer filled up the porous structure of the painted layer and covered the pigment particles. These findings demonstrate that aqueous, water-borne fluoropolymer can be used as an adhesive agent for micron cracks. Meanwhile, via the operating platform of the optical imaging monitoring system, the micron cracks of the painted terracotta warriors and horses from the Western Han Dynasty were successfully repaired using the water-borne fluoropolymer. The results imply that the microstructure, size, and geometric spaces of the cracks can be obtained directly utilizing microscopic imaging technology. The dynamic monitoring and imaging system described above can be employed to assist prosthetists in visualizing micro-repair operations in real time, assist with fine visual operations during the repair process, and realize dynamic video recording of the entire repair process. Our work provides a simple visualization method to repair micron-scale cracks in painted pottery relics by applying modern fluoropolymer and ultra-depth-of-field digital microscopic imaging technology.

An Essential Role of Polymeric Adhesives in the Reinforcement of Acidified Paper Relics.

Paper acidification causes paper relics to undergo embrittlement and decay, to form dregs, and even to break upon a single touch; therefore, reinforcement and deacidification treatments are essential steps for paper conservation and to retard the deterioration and prolong the life of objects. Polymeric adhesives play an essential role in reinforcement and deacidification treatments, although it is not well studied. In this work, the effect of polymeric adhesives on the conservation process and their protective effects on acidified paper relics were studied. Firstly, three polymeric adhesives, including wheat starch paste, polyvinyl butyral (PVB), and polyvinyl alcohol (PVA), were selected as research objects. Subsequently, their effects on four popular conservation methods were further discussed, including traditional mounting, hot-melt with silk net, alcohol-soluble cotton mesh, and water-soluble cotton mesh. Additionally, as an example, the reversibility and long-term durability of water-soluble adhesive PVA-217 were assessed. Using a computer measured and controlled folding endurance tester, pendulum tensile strength tester, tear tester, burst tester, FT-IR, video optical contact angle tester, and other instruments, the conservation application of water-soluble adhesives in paper relics was evaluated. This study provides a scientific basis and experimental data for the application of polymeric adhesives in the conservation of paper relics.

An Essential Role of Gelatin in the Formation Process of Curling in Long Historical Photos.

Curling disease in long historical photos significantly affects the presentation of cultural heritage information. However, people lack attention to the formation process and microstructural changes of photo curling. In this article, a long historical photo (1912-1949 AD) collected by the Second Historical Archives of China was taken as the research object, and the formation process and cause of the curling were further explored. Firstly, Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray energy disperse spectrometer (EDS), and other instruments were used to analyze the material composition of the long historical photo. It was found that the photographic paper was made of gelatin, barium sulfate, and plant fiber layers. Then, the effects of hygrothermal environments on curling and contraction in the gelatin layer and simulated photographic paper were explored. Meanwhile, the formation process and main influence factors of the curling were preliminarily revealed. The morphological analysis by SEM was carried out to identify the inner correlation between the microstructure and curling of photos. Finally, the possible formation cause of photo curling was analyzed. This study provides a scientific basis and experimental data for the preservation and restoration of long historical photos based on gelatin.

Strained Endotaxial PbS Nanoprecipitates Boosting Ultrahigh Thermoelectric Quality Factor in n-Type PbTe As-Cast Ingots.

Lead telluride (PbTe) has long been regarded as an excellent thermoelectric material at intermediate temperature range (573-873 K); however, n-type PbTe's performance is always relatively inferior to its p-type counterpart mainly due to their different electronic band structures. In this work, an ultrahigh thermoelectric quality factor (µ/κL  ≈ 1.36 × 105 cm3 KJ-1 V-1 ) is reported in extra 0.3% Cu doped n-type (PbTe)0.9 (PbS)0.1 as-cast ingots. Transmission electron microscopy (TEM) characterization reveals that excess PbS exists in PbTe matrix as strained endotaxial nanoprecipitates, which affect electrical and thermal conduction discriminately: (1) coherent PbTe/PbS lattice minimizes the interface scattering of charge carriers; (2) periodic strain centers at PbTe/PbS interface exhibit intensive strain contrast, which can strongly scatter heat-carrying phonons. Electron backscattered diffraction (EBSD) characterization illustrates very large PbTe grains (≈1 mm) in these as-cast ingots, ensuring an extremely low grain boundary scattering rate thus a very high charge carrier mobility. Eventually, a remarkably high ZTmax  ≈ 1.5 at 773 K and an outstanding ZTavg  ≈ 1.0 between 323 and 773 K are simultaneously achieved in the (PbTe)0.9 (PbS)0.1  +0.3%Cu sample; these values are highly competitive with reported state-of-art n-type PbTe materials.

First-principles calculations of electrical properties, structure, and phase transition of K1-xNaxNbO3 solid solutions.

The structure, total energy and orthorhombic as well as tetragonal electronic properties of K1-xNaxNbO3 (KNN) as a function of Na concentration were studied with first principles calculations. When the Na content of KNN was gradually increased the orthogonal phase transformation occurred, which produced an enhanced piezoelectric response of the tetragonal KNN. This result proved that the high d33 originated from the phase transition. The corresponding calculations reveal that the change of Nb-O bond length is the origin of distortion of Nb-O octahedral and phase transition. In addition, the calculations observed an unusual high peak of the KNN piezoelectric parameter, which showed the same trend as the experimental results.