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Human activities impose significant changes on sedimentation processes and vegetation cover within lake catchments. However, the needed time for an anthropogenically disturbed natural state to be reversed back to its natural state by environmental protection programs is still ambiguous. Here we employ a multi-proxy approach to delineate major environmental disturbances such as logging and forest fires on the catchment in Cueifong Lake, a subtropical subalpine lake in northeastern Taiwan. X-ray Fluorescence (XRF) core scanning, bulk total organic carbon (TOC), bulk total nitrogen (TN), stable carbon isotope (δ

Resolved measurements of the relative abundances of 13CDH3 and 12CD2H2 from a Taiwan mud volcano confirm that thermogenic CH4 with a formation temperature of 150 °C is bubbling from a pool of liquid mud. Analysis for both doubly-substituted molecules provides confirmation that isotopic exchange equilibrium was achieved between methane isotopologues. Methane extracted from the headspace of core samples taken from sediments deposited proximal to the bubbling pool of mud shows small departures from isotopic equilibrium.

The isoscape of particulate organic matters (POM) in the euphotic zone at the shelf of the East China Sea (ECS) is affected by hydrological interactions and biological activities. Based on the stable carbon and nitrogen isotope values (δ13C and δ15N) and C:N ratio of POM (0.7 to 50 μm) in the euphotic zone of the ECS from 2008 to 2018 with a total of 113 samples, we inferred their sources and then investigated what hydrographical and biological conditions determined these spatio-temporal variations through synoptic and intensive seasonal monitoring. The isotopic signatures (δ13C: −26.9 to −12.4‰, δ15N: −1.0 to 10.8‰) and C:N ratios (4.4–9.0) of euphotic POM varied within the range of values reported for marine phytoplankton, suggesting limited contribution of terrigenous POM to the shelf of the ECS. The δ13C values of POM increased with the increase of chlorophyll-a (chl-a) concentration at the depth of chl-a maximum and the δ15N values decreased near the Changjiang River plume and inner shelf with freshwater input and coastal upwelling in summer. This indicated that phytoplankton production was enhanced by high nutrient supply and warmer temperature. Besides, the δ15N values were higher under lower inorganic nitrogen nutrient concentrations, and were negatively correlated with POM C:N ratio (i.e., δ15N value was less negative with higher nitrogen content in POM). Such correlations may suggest the enhanced trophic interactions in microbial food chains in oligotrophic environments, where phagotrophic protists with high δ15N values could be included into the size fraction (0.7–50 μm) of POM. Based on our study, the spatial and temporal δ13C and δ15N isoscape of euphotic POM serves as an ecological indicator to infer primary production and plankton food web properties of the East China Sea.

The Chingshui geothermal field, a moderate-temperature and water-dominated hydrothermal system, was the site of the first geothermal power plant in Taiwan. Many geological, geophysical and geochemical studies using more than 21 drilled wells have been performed since the 1960s. However, there are still controversies regarding the heat and fluid sources due to the tectonically complicated geological setting. To clarify the heat and fluid sources, we analyzed clumped isotopes with carbon and oxygen isotopic compositions of calcite scaling in geothermal wells and veins on outcrops and calculated the δ 18 O values of the source fluids. Two populations of δ 18 O values were calculated: −5.8 ± 0.8‰ VSMOW from scaling in the well and −1.0 ± 1.6‰ to 10.0 ± 1.3‰ VSMOW from outcropping calcite veins, indicative of meteoric and magmatic fluid sources, respectively. Meanwhile, two hydrothermal reservoirs at different depths have been identified by magnetotelluric (MT) imaging with micro-seismicity underneath this area. As a result, we propose a two-reservoir model: the shallow reservoir provides fluids from meteoric water for the scaling sampled from wells, whereas the deep reservoir provides magmatic fluids from deep marble decarbonization recorded in outcropping calcite veins.

In this study, we analyzed the carbon and nitrogen stable isotopic composition of human bone collagen in 33 individuals found at the Fantzuyuan site in Taiwan in order to investigate the dietary patterns of this Iron Age group. Forty-three faunal collagen samples were also analyzed to ascertain the variability of baseline isotopic signatures in the area. Mean δ13C and δ15N values of − 12.5 ± 0.7‰ and 8.1 ± 0.5‰, respectively, were found in 26 human individuals. In conjunction with archaeological evidence, this study showed that human diet at this site derived mainly from terrestrial animals, with a minor component derived from marine shellfish. No significant difference in isotopic compositions was detected between male and female adults or between adults and juveniles. However, six individuals had dietary patterns that were different from others, which probably reveals that they had special social status and/or non-local origins.

Radiocarbon has been widely used in determining the age of various geological materials and events. The validity of ages, particularly for sediments, has often been questioned due to the incorporation of carbon-bearing components with different abundances of 13 C and 14 C. This study examines carbon contained in clay minerals (kaolinite, illite and illite-smectite) extracted by temperature-stepped combustion experiments, ranging from 350 °C to 1100 °C. Distinct carbon components were identified in the samples using both their 13 C and 14 C contents. Two carbon end-members were observed for all of the clay minerals: a low temperature component ( 13 C and enriched in 14 C; and a high temperature component (>550 °C), relatively enriched in 13 C and depleted in 14 C. The high temperature carbon component is relatively old and not released until the clay is completely oxidized. This observation suggests that this carbon was incorporated into the clay mineral when it first formed by weathering. We applied the same procedure to sediments collected from terraces along the Kueichung River, in southwestern Taiwan, sieved to

Carbon and nitrogen stable isotope analyses were conducted on Neolithic Yuan-Shan faunal bone collagen to reconstruct a site-specific dietary isotope baseline, and to evaluate the contribution of potential food resources to the diet of Yuan-Shan people. The mean δ 13 C and δ 15 N values of terrestrial mammals were − 17.7 ± 3.6‰ and 5.4 ± 1.3‰, respectively. The mean δ 13 C and δ 15 N values of freshwater fish were − 20.8 ± 2.2‰ and 7.7 ± 2.0‰; while the marine fish had the highest mean δ 13 C (− 11.8 ± 1.2‰) and δ 15 N values (12.1 ± 1.7‰). Combined with archeological evidence and previous isotopic data derived from Yuan-Shan human bone collagen, we suggest that the subsistence strategies of Yuan-Shan people were broad. They relied on rice cultivation, hunting, fishing and gathering food resources from the wild; in addition, they probably raise pigs, as early as 4200 yr BP. Although the Yuan-Shan people relied on broad-spectrum food resources, the foods they mainly consumed were terrestrial herbivores and freshwater fish based on the result of multi-source mixing model. Besides, marine fish, shellfish, and C 3 plants also contributed substantially to their diet. By comparison, the contribution of C 4 plants was minor.

The Tengchong volcanic field, located at the collision zone between the Indian and Eurasian plates, is well known for its large-scale Holocene volcanic eruptions and extensive hydrothermal activities. Bubbling gases from eight geothermal springs at the Tengchong field were collected and analyzed for their chemical and isotopic compositions (3He/4He, 20Ne, N2, Ar, δ13CCH4 and δ13CCO2). The results show that the gas samples could be categorized into a group I dominated by N2 and a group II with CO2 as major component. The air-corrected 3He/4He ratios ranged from 0.17 Ra to 4.76 Ra and the calculated mantle contributions dramatically varied from 1.9% to 77.9% for group II. By contrast, an invariant air-corrected 3He/4He ratio of about 0.30 Ra and a relatively constant mantle contribution of 4.0% to 5.0% was obtained for group I. The sampling sites just on top of the magma chamber received significant mantle-derived helium and magmatic gas components (at the proximal site of the magma chamber: >95% magmatic gas contributions). The calculated N2/Ar ratio of the hydrothermal endmember for group II (sample sites close to the magma chamber) was 61.7–66.2, suggesting that the reaction zone temperature is between 223 °C and 252 °C. The influence of the magma chamber decreases with increasing distance of the sampling sites from the chamber apex. The sampling sites (group I) at the marginal area discharge gases with relatively low 3He/4He ratios and magmatic contributions (19–24%). The temperature of the reaction zone for this group was estimated to be 74 °C based on the N2/Ar ratio of 42. This study provided important constraints to relate hydrothermal gas geochemistry directly with the spatial distribution of the underlying magma chamber. Plain language summary Geochemical characteristics of gases discharged from hydrothermal systems are usually affected by deep magmatic processes, shallow hot fluids circulation, and water-rock interactions in the reaction zone. In this study, we analyzed the gas abundances and isotopic compositions of hydrothermal gas discharged from the Yunnan-Tibet geothermal belt. We used a gas mixing model to quantify the contributions of mantle-derived/magmatic endmember and hydrothermal endmember. The 3He/4He ratios, magmatic contribution, and temperature of the reaction zone decreased significantly with increasing distance from the magma chamber underneath the Tengchong field, highlighting the intimate relationships between gas transport, hydrothermal circulation and the extent of the magma chamber.

Summary This study evaluated the biogeochemical interactions between arsenic (As) and sulfur (S) in groundwater to understand the natural and anthropogenic influences of S redox processes on As mobilization in the Lanyang Plain, Taiwan. Cl − and the sulfate isotopic composition δ 34 S [ SO 4 ] were selected as conservative tracers. River water and saline seawater were considered as end members in the binary mixing model. Thirty-two groundwater samples were divided into four types of groundwater (I, pyrite-oxidation; II, iron- and sulfate-reducing; III, sulfate-reducing; and IV, anthropogenic and others). The binary mixing model coupled with discriminant analysis was applied to yield a classification with 97% correctness, indicating that the DO/ORP values and δ 34 S [ SO 4 ] and Fe 2+ concentrations are effective redox-sensitive indicators. Type I groundwater is mostly located in a mountainous recharge area where pyrite oxidation is the major geochemical process. A high 18 O enrichment factor e [ SO 4 – H 2 O ] and high 34 S enrichment factor e 34 S [ FeS 2 – SO 4 ] indicate that disproportionation and dissimilatory sulfate reduction are both involved in Type II and Type III groundwater. The process of bacterial sulfate reduction may coprecipitate and sequester As, a mechanism that is unlikely to occur in Type II groundwater. The presence of high As and Fe 2+ concentrations and enriched δ 34 S [ SO 4 ] in Type II groundwater suggest that biogeochemical reactions occurred under anaerobic conditions. The reductive dissolution of As-bearing Fe oxyhydroxides together with microbial disproportionation of sulfur explains the substantial correlations among the high As concentration and enriched δ 34 S [ SO 4 ] and Fe 2+ concentrations in the iron- and sulfate-reducing zone (Type II). The As concentration in Type III groundwater (sulfate-reducing) is lower than that in Type II groundwater because of bacterial sulfate reduction and coprecipitation with As. Furthermore, the dissolution of sulfate minerals is not the major source of aqueous SO 4 , based on the sulfur isotopic composition of solid-phase sulfate (δ 34 S [sulfate mineral] ). Finally, the anthropogenic influence of fertilizers with wide S isotopic ranges is proposed as the plausible sulfate budget in Type IV groundwater. The results of this study suggest that the As release into groundwater involves the reductive dissolution of As-bearing Fe-hydroxides, bacterial sulfate reduction, and microbial disproportionation in the Lanyang Plain.

Temperamental tendencies may form the basis of personality development, and specific personality constellations are associated with increased incidences of behavioural problems. Phthalic acid ester (PAE) has been associated with symptoms of attention deficit hyperactivity disorder (ADHD) in cross-sectional studies. We hypothesised that early-life exposure to PAE affects the temperaments of children, particularly ADHD traits. In this study, we analysed the temperament evaluations completed at least once by maternal–infant pairs (n = 208) when the child was aged 2, 5, and/or 11 years between 2000 and 2012. We measured seven PAE metabolites in the urine of the mothers during pregnancy and their children using liquid chromatography-electrospray ionisation-tandem mass spectrometry. These metabolites included mono-methyl phthalate, mono-ethyl phthalate, mono-butyl phthalate (MBP), mono-benzyl phthalate (MBzP), and three metabolites of di (2-ethylhexyl) phthalate. The phthalate metabolite levels in pregnant women were significantly associated with a decreased threshold of responsiveness (coefficients from −0.21 to −0.46) and increased distractibility (coefficients from 0.23 to 0.46) in pre-school children. After adjustment for maternal exposure, the phthalate metabolite concentrations of the children exhibited significantly increased odds ratios (ORs) with respect to the ADHD symptom traits. Specifically, mono-2-ethyl-5-hydroxyhexyl phthalate (MEHHP), the sum of the DEHP metabolites, and MBzP yielded ORs and 95% confidence intervals of 2.98 (1.05–8.48), 3.28 (1.15–9.35), and 9.12 (1.07–78.06), respectively, for every log10 creatinine unit (g/g creatinine) increase. Thus, early-life phthalate exposure was found to be associated with the behavioural characteristics of children, particularly temperamental traits associated with ADHD.

High arsenic concentration in groundwater is influenced by redox reactions in As-bearing iron (oxy)hydroxide minerals and elevated total organic carbon, resulting in arsenic contamination and enrichment in groundwater after introduction of seawater into an aquifer. In this study, hydrochemical and isotopic (S, O and C) techniques were used to relate arsenic contamination and seawater flooding/intrusion in groundwater aquifers in the Chianan Plain, southwestern Taiwan. Thirty-three samples (30 from groundwater and 3 from river water) were collected from April–June of 2014. Most of the groundwater samples collected from the Chianan Plain were dominated by As(III), indicating that reducing conditions prevailed within the aquifers. The δ18O-δD plots of most of the groundwater samples from the Chianan Plain are generally lined on the global meteoric water line (GMWL), but the δ18O and δD isotopic compositions of the river water samples show enriched signals. Salinity and sulfate concentrations of river water and shallow groundwater have been found to increase after seawater flooding/intrusion. The δ18O and δD isotopic compositions of the river water showed a gradual trend toward those of seawater. The trend in the isotopic compositions of the river and groundwater samples indicated a mixing of seawater and meteoric water. Up to the present, the groundwater levels in the coastal areas of the Chianan Plain have dropped to zero meters in elevation parallel to sea level due to excessive groundwater withdrawal, resulting in seawater intrusion into the aquifers in Budai, Yichu, and Beimen in the Plain. Moreover, high salinity (48.1‰) occurred only in the Beimen 2B shallow groundwater at a depth of 60 m is a result of seawater flooding infiltration from the nearby salinized Pachang River. The δ34S[SO4]/δ18O[SO4] isotopic ratios (2.63–2.82) of low-As (concentration

summary This study explores the distribution and mobilization of As in the ecosystem of the Guandu wetlands, Taiwan. The chemical parameters, chemical sequential extraction, mineralogical compositions, and sulfur isotopic compositions (i.e., d 34 S½SO4� and d 18 S½SO4� ) of porewater and two sediment core samples (S2 and S5, locate in the inner and outer sites of the Guandu wetland) were analyzed to characterize As spatial distribution. The crucial mechanisms of the biogeochemical processes that control As mobility in wetland ecosystems were inferred. Based on factor analysis and cluster analysis, the vertical distributions of the redox zones in S2 and S5 were classified as oxidizing, transitional, and reducing zones, respectively. The mineralogical characteristics showed that adsorption and desorption are the major processes which control As retention in the surface sediment under cyclic aerobic/anaerobic conditions. Aqueous As and Fe were restrained because of oxidation, whereas aqueous Fe precipitated as amorphous metal oxides (i.e., FeO, FeOOH, and Fe2O3). Subsequently, aqueous As was adsorbed onto the surfaces of Fe(hydr)oxides, resulting in a high solid As content in the oxidizing zone. The high aqueous As content in the boundary of the transitional and reducing zones was caused by the reductive dissolution of highly dissolved Fe compounds through the microbial respiration of organic matter (OM). In the reducing zone, As 3+ can be constrained by the formation of FeS2 in sediment during bacterial sulfate reduction that is governed by the relative enrichment of the d 34 S½SO4� and d 18 S½SO4� values. Sulfur disproportionation and the redox of ele

Hydrocarbon seepage is a surface expression where fluids mixed with sediments and hydrocarbons are expelled through fracture systems that potentially tap into gas–petroleum reservoirs. Hydrocarbons released from most seeps appear to be thermogenic on the basis of their relative abundance and isotopic composition. The potential for subsurface microbial processes modifying these geochemical fingerprints remains poorly constrained. In this study, microcosm incubations were conducted on mud slurries supplied with/without various methanogenic precursors at temperatures ranging from ambient conditions to 90 °C, in order to assess microbial CH4 formation in the subsurface beneath hydrocarbon seeps. The analyses indicated that CH4 production was positive at ⩽80 °C, regardless of whether or not or which precursors were added. However, the pattern of CH4 production rates varied with the precursor and temperature. In general, the optimum CH4 production from H2/CO2 and formate occurred over a wide range of temperatures (⩾40 °C), whereas that from acetate, methanol and methylamine was restricted to relatively lower temperatures (40–50 °C). The CH4 recoveries, together with the C isotopic compositions of CH4, further indicated that the quantities of CH4 produced could not completely account for the quantities of precursor consumed, suggesting that a complex metabolic network was involved in the transformation of the added precursor and organic C inherited from inoculated sediments. Microbial CH4 was estimated to constitute 7–61% of the CH4 observed using experimentally-derived apparent isotope fractionations as the end member compositions. This illustrates the possibility that microbial CH4 produced at shallower depths could quantitatively and isotopically alter deeply-sourced thermogenic CH4 in hydrocarbon seep environments.

Densifications of hot-pressed ZrC ceramics with Zr and graphite additives were studied at 1800–2000 °C. ZrC with 8.94 wt% Zr additive (named ZC10) sintered at 1900–2000 °C achieved higher relative densities (>98.4%) than that of additive-free ZrC (

The PoSen complex, located closely adjacent to the southwestern margin of the Red River shear zone represents the uplifted basement of north Vietnam and may record the motion of the shear zone. However, its thermochronological history has not been fully examined yet. Here we applied U–Pb and 40 Ar/ 39 Ar dating methods to reveal its thermochronological history. U–Pb analysis of composite zircon grains by TIMS yielded an average age of 760 ± 25 Ma, clustering on the concordia line. Twelve SHRIMP U–Pb analyses also yielded a consistent result of 751 ± 7 Ma. Along with the geochemical features, the U–Pb dating results suggest the PoSen complex was a late Proterozoic magmatic complex, which could correspond to the Chengjiang orogeny, a widespread thermal event in southwest China. Results of 40 Ar/ 39 Ar dating of micas and K-feldspars were in the range of 36–30 Ma, revealing a rapid cooling and exhumation history of the PoSen complex during the late Paleogene. The time span of cooling and exhumation of the PoSen complex is slightly older than the main cooling phases of the Ailao Shan–Red River (ASRR) metamorphic massifs (28–17 Ma), but is synchronous with the early igneous activity stage in the eastern Indo-Asian collision zone of southeast China and north Vietnam. Owing to the ongoing debate about the initiation and offset of the ASRR shear zone, the tectonic force for the late Paleogene cooling of the PoSen complex is still inconclusive. The rapid exhumation of the PoSen complex could be in response to either the detachment of the Neo-Tethyan slab or a transpressional phase of continental subduction along the ASRR shear system in the eastern Indo-Asian collision zone.

The influence of the spark plasma sintering (SPS) heating rate on densification, microstructure and strength of ZrB2–20 vol.% SiC composites with or without 5 vol.% Yb2O3 addition was assessed. A low heating rate promoted densification, induced grain growth and slightly increased the strength in the Yb2O3-free ceramics, whereas the low heating rate inhibited the densification, maintained the grain size and greatly decreased the strength in the Yb2O3-doped composites.

Using three elementary substances, Mo, Ni, and amorphous B powders as raw materials, the ternary boride based hard alloy Mo2NiB2–Ni was prepared successfully. The formation mechanism of the ternary phase was verified by XRD. It was indicated that the formed Mo2NiB2 particles at lower temperatures could be as seeds for the further formation of Mo2NiB2 directly from the raw materials of Mo, Ni and B at higher temperatures. The appearance of liquid phases between 1100 and 1200 °C was important for the densification of hard alloy. The microstructures of the hard alloys were observed by SEM. The main fracture modes for the hard alloys were different for the samples sintered at different temperatures. The maximum bending strength and the Rockwell hardness reached 1.85 ± 0.04 GPa and 85.7 ± 0.1 HRA, respectively. These values were comparable to those reported in literature.

The ball-milling process is a usual route employed to break up agglomerates in the powder or mix the powder with additives when preparing ceramics. Although it is well known that a powder can be “contaminated” by the wear particles from the milling balls, the study dealing with how the preparation and properties of a hard material would be affected by additives just introduced by scrape of milling balls has been scarce. In the present work, sintering behavior and mechanical properties of hot-pressed B 4 C with additives derived from milling balls were investigated. Polyoxymethylene, ZrO 2 , Al 2 O 3 and Si 3 N 4 were selected as different ball materials. The results show that the sinterability of B 4 C could be significantly enhanced because of the incorporation of one of these additives, i.e. ZrO 2 , Al 2 O 3 and Si 3 N 4 (approximately 3–6 vol%). As a result of improvement in density, excellent mechanical properties of B 4 C ceramics were obtained. Among them a flexural strength of B 4 C added by ZrO 2 reached 630 MPa.

ZrB 2 –20 vol% SiC composites with 3 vol% Re 2 O 3 rare-earth oxide (Re = La, Nd, Y or Yb) were hot pressed to near full-density at 1900 °C. The La 2 O 3 and Nd 2 O 3 additions not only caused the formation of an amorphous grain boundary phase and enhanced densification, but also resulted in substantial ZrB 2 and SiC grain growth. In contrast, the Y 2 O 3 and Yb 2 O 3 additions resulted in the formation of crystalline (Y/Yb) 2 Zr 2 O 7 and enhanced densification without ZrB 2 and SiC grain growth. The hardness was improved by the rare-earth oxide addition, especially with Y 2 O 3 and Yb 2 O 3 . The La 2 O 3 and Nd 2 O 3 only had a minor effect on the fracture toughness, whereas the Y 2 O 3 and Yb 2 O 3 additions increased the fracture toughness. The type of Re 2 O 3 addition was found to influence the nature of the grain boundary and the concomitant fracture and toughening mechanisms.

Using Si and BN powders as raw materials, silicon nitride/hexagonal boron nitride (Si 3 N 4 /BN) ceramic composites were fabricated at a relatively low temperature of 1450 °C by using the reaction bonding technology. The density and the nitridation rate, as well as the dimensional changes of the specimens before and after nitridation were discussed based on weight and dimension measurements. Phase analysis by X-ray diffraction (XRD) indicated that BN could promote the nitridation process of silicon powder. Morphologies of the fracture surfaces observed by scanning electron microscopy (SEM) revealed the fracture mode for Si 3 N 4 /BN ceramic composites to be intergranular. The flexural strength and Young's modulus decreased with the increasing BN content. The reaction-bonded Si 3 N 4 /BN ceramic composites showed better machinability compared with RBSN ceramics without BN addition.

ZrB2–20 vol.% MoSi2 composites with elongated ZrB2 grains were prepared by reactive hot pressing using Zr, Si, B and Mo as raw materials. The ductile behavior of MoSi2 at high temperature helped the rod-like ZrB2 grains align under the applied pressure during sintering, resulting in a partly textured composite. The anisotropic growth of ZrB2 grains improved the toughness of the composite remarkably.

Three ZrB2–SiC composites were prepared from polycarbosilane (PCS)-coated ZrB2 powders. Powders with or without additions of Si or Zr were densified by hot pressing at 1800 °C. Finally, the oxidation resistance of the composites was studied at 1500 °C in air. The phase composition and microstructure were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) along with energy-dispersive spectroscopy (EDS). Results showed that Si addition, which reacted with free carbon coming from the pyrolyzed PCS to produce the SiC, improved the oxidation resistance of ZrB2–SiC composites with PCS as a precursor, whereas Zr addition, which reacted with the carbon to produce the ZrC, decreased it.

The isothermal oxidation of ZrB 2 powder was carried out in the range of 650–800 °C in a flowing air using thermogravimetric analysis (TGA). The evolution of the phase characterization and morphology of ZrB 2 powder oxidized at 700 °C for varying durations was studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The excellent fit of TG curves by multiple-law model suggests that the oxidation of ZrB 2 powder in air follows para-linear kinetics, and based on the fitted results, oxidation mechanisms can also be obtained. The reaction product of ZrB 2 powder with oxygen is metastable tetragonal ZrO 2 at 700 °C, and the tetragonal phase transforms to the monoclinic phase with oxidation. The oxidation of ZrB 2 powder is associated with surface microcrack formation, which is attributed to volume expansion resulting from oxidation of ZrB 2 to tetragonal ZrO 2 and tetragonal-to-monoclinic phase transformation of ZrO 2 . In the last stage of oxidation, each ZrB 2 particle breaks into fragments.

A suspension stabilizer-coating technique was employed to prepare x mol% Yb2O3 or Gd2O3 (x = 1.0, 2.0, 3.0 and 4.0) co-stabilized 1.0 or 2.0 mol% Y2O3 doped ZrO2 nanopowders (xYb1Y, xYb2Y, xGd1Y). Fully dense Yb2O3/Gd2O3 and Y2O3 co-doped ZrO2 ceramics were obtained by means of pressureless sintering in air at 1450 °C. Phase assemblage, microstructure measurements indicated that polycrystalline tetragonal ZrO2 (TZP) was achieved in the 1Yb1–2Y and 1Gd1–2Y grades, whereas the 4Yb1–2Y ceramic was almost fully stabilized cubic ZrO2 (FSZ) and all other investigated stabilizer combinations resulted in partially stabilized zirconia (PSZ). Complex impedance analysis showed that the conductivity of the xGd1Y and xYb1–2Y co-doped zirconia ceramics increased with increasing Gd2O3 and Yb2O3 content. The xGd1Y grade had a lower conductivity than the xYb1Y and xYb2Y ceramics. The conductivity behaviour was assessed and explained in terms of the cubic phase content and dopant ionic radius.

Adding a small amount of vanadium carbide as sintering aids, nearly fully dense ZrB2–SiC composites were obtained by pressureless sintering methods at 2000–2100 °C. Thermodynamic calculations and experimental results proved that VC is better at removing the surface oxide impurities of ZrB2 than WC, and played a very important role during the densification process. The mechanical properties of the sintered ceramics were also reported.

Cr 2 AlC powders prepared by the molten salt method, using chloride as the fluxes, were successfully obtained. The influences of composition, weight ratio of powder to flux and temperature on phase assembly and morphology of Cr 2 AlC powders were investigated. The results indicated that the amount of Cr 2 AlC increases as powder/flux ratio decreases from 2:1 to 1:1 while the further decrement of powder/flux ratio to 1:2 has little effect on its amount. As the excessive Al in elemental powders increases from 0 to 10 at.%, the amount of Cr 2 Al increases greatly and the Cr 7 C 3 content decreases obviously. The amount of Cr 2 AlC increases evidently with the obvious decrease of Cr 2 Al and the slight reduction of Cr 7 C 3 as temperature raises from 900 to 1000 °C while a further increase in temperature has limited effect on their amount. The results of scanning electron (SE) observation on fabricated Cr 2 AlC powders indicate that the liquid phase content in composition is the critical influencing factor on the morphology. Predominantly single-phase powders of Cr 2 AlC are fabricated and its sintering ability is also studied.

ZrB 2 –20 vol%SiC ceramics without and with additive of 2 wt% carbon nanotubes (CNTs) were fabricated by hot-pressing at 1900 °C for 1 h under 30 MPa using ZrB 2 , SiC and CNTs as starting materials. The fracture toughness increased about 15%, but hardness, flexural strength as well as thermal conductivity did not vary significantly from the addition of CNTs.

Bi 3.15 Nd 0.85 Ti 3 O 12 ceramic, which is a three-layer ferroelectric Aurivillius phase, was prepared by spark plasma sintering. The effect of texture on the anisotropy of dielectric, ferroelectric and piezoelectric properties was studied. X-ray diffraction showed that samples perpendicular to the hot-pressing direction had a – b -axis preferred texture, whereas, samples parallel to hot-pressing direction had c -axis preferred orientation. The dielectric constant, remanent polarization and piezoelectric constant of samples with orientation close to a -axis are larger than those of samples with orientation close to c -axis. Their Curie points are all about 410 °C.

Neodymium-modified bismuth titanate (BNT) powder with compositions of Bi 4− x Nd x Ti 3 O 12 ( x = 0, 0.2, 0.5 and 0.75) were prepared through a hydrolysis method. The influence of Nd addition on the powder characteristics, sintering, microstructure and properties were investigated. It was found that the absorption band of Ti–O stretching vibration at 589 cm −1 was shifted to a higher wave number in the IR spectra, and the sintering as well as grain growth was significantly retarded. The Curie temperature, dielectric loss and Curie peak intensity were steadily decreased with an increase in Nd concentration, and the dielectric constant and loss tangent became much less dependent on temperature and frequency. At the same time, the polarization properties of the material were greatly improved.

The investigation of bulk Cr2AlC ceramic fabricated by Spark Plasma Sintering (SPS) from coarse powders (CAC10) and fine powders (NCAC10) in the temperature range of 1100–1400 °C was carried out. The XRD results indicate that Cr2AlC, as major phase, always appears with minor and trace amount of Cr7C3 and Cr2Al respectively in both NCAC10 and CAC10 samples and the amounts of later two phases decrease with increase in temperature. However, the Cr2AlC phase content in NCAC10 is higher than that of CAC10 sintered at the same temperature. The micrographs of back-scattered SEM show that grains with smaller size and pores with fewer amounts appear in SPSed NCAC10 in comparison to that of CAC10. As consequence, the higher hardness (5.6 GPa) of NCAC10 than that (3.9 GPa) of CAC10 was obtained. The patterns of XRD, microstructure and hardness of samples HPed at 1400 °C for the same composition were also presented for comparison. © 2007 Elsevier B.V. All rights reserved.

Four kinds of composites, ZrB2–SiC, ZrB2–SiC–ZrC, ZrB2–SiC–ZrN and ZrB2–SiC–AlN, were synthesized in situ via reactive hot pressing (RHP) and reactive spark plasma sintering (R-SPS), using Zr, Si, B4C, BN and Al as raw materials. The synthesis process plays a critical role in the microstructural features of the composites obtained. The R-SPS process can lead to a more homogeneous and finer microstructure due to its high heating rates and short holding time, while the RHP process is likely to result in coarse microstructures due to a long enough holding time for grains growth.

Nd/V co-doped Bi4Ti3O12 ceramics, Bi4−yNdyTi2.98V 0.02O12.01 (BNTV, y = 0.16 , 0.26, 0.36 and 0.56), were prepared using a solid-state reaction method and their phase assemblages, microstructure, dielectric and ferroelectric properties were investigated. The Curie temperature of BNTV ceramics decreases with increasing Nd concentration. The loss tangent of the materials is much lower (1.8% at 400 ∘C/100 kHz for BNTV0256) than that of BIT sample (77%). Besides, BNTV ceramics exhibit saturated ferroelectric hysteresis loops with 2Pr of 26–31 μC/cm2 and Ec of 41–57.5 kV/cm.

ZrB 2 –SiC–C ultra high temperature ceramics (UHTCs) have been produced by hot pressing pyrolyzed mixtures of ZrB 2 and polycarbosilane (PCS). Samples with SiC contents of 0%, 5% and 16% in volume derived from PCS were prepared. The phase composition, microstructure and mechanical properties were characterized for composites hot pressed at 2073 K for 60 min under the pressure of 20 MPa in an argon atmosphere. Analysis showed that the addition of PCS improved the relative density from 78% (without PCS addition) to ∼ 100% (with 16% SiC derived from PCS addition). Hardness and fracture toughness of the composite were also improved.

A stabiliser coating technique was applied to prepare mixed Nd2O3 +Y 2O3 coated ZrO2 nanopowder from an alcohol/water based suspension of neodymium nitrate, yttrium nitrate and monoclinic zirconia nanopowder. The mixed stabiliser starting powders could be fully densified into (Nd,Y)TZP ceramics by pressureless sintering in air at 1450 ◦ C. The obtained ceramics revealed an excellent fracture toughness up to 12.8 MPa m 1/2 in combination with a hardness of 11 GPa, a toughness that is comparable to that of the traditional 12 mol CeO2-stabilised TZP but with higher hardness.

The reaction process of Cr 2 AlC ceramics was analyzed, in which the samples were prepared for composition Cr:Al:C = 1:1.2:1 by hot-pressing in argon in the range of 850–1450 °C using Cr, Al and graphite powders as the starting materials. X-ray diffraction (XRD), electron probe microanalysis (EPMA) and energy dispersive spectrum (EDS) were employed for identification of phase assembly and analysis of reaction route of the samples. The phase formation sequence of Cr 2 AlC was finally analyzed based on phase diagram of the Cr–Al binary system combined with the results of differential thermal analysis (DTA) and XRD. It was found that Cr 5 Al 8 , Cr 2 Al and Cr 7 C 3 were the intermediate phases appearing in turn in the heating process. The amount of Cr 2 AlC phase was gradually increased with increase in temperature by the reaction between Cr–Al intermetallic compounds, un-reacted Cr and graphite, and it became a pure phase in the sample with disappearance of intermediate phases above 1250 °C.

Cr2AlC ceramics were fabricated by hot-pressing using Cr, Al and C powders as starting materials. The phase assemblages of the samples consisted of Cr2AlC, as a major crystalline phase, together with a very small amount of Cr7C3 and an unknown phase. Its thermal and electrical as well as mechanical properties were determined.

Nano-powders of BaTiO3, SrTiO3, Ba0.6Sr0.4TiO3, a mixture of the composition (BaTiO3)0.6(SrTiO3)0.4 with particle sizes in the range of 60 to 80 nm, and Bi4Ti3O12 with an average particle size of 100 nm were consolidated by spark plasma sintering (SPS). The kinetics of reaction, densification and grain growth were studied. An experimental procedure is outlined that allows the determination of a “kinetic window” within which dense nano-sized compacts can be prepared. It is shown that the sintering behaviour of the five powders varies somewhat, but is generally speaking fairly similar. However, the types of grain growth behaviour of these powders are quite different, exemplified by the observation that the kinetic window for the (BaTiO3)0.6(SrTiO3)0.4 mixture is 125 oC, ~75 oC for Bi4Ti3O12, ~25oC for BaTiO3 and SrTiO3, while it is hard to observe an apparent kinetic window for obtaining nano-sized compacts of Ba0.6Sr0.4TiO3. During the densification of the (BaTiO3)0.6(SrTiO3)0.4 mixture the reaction 0.6BaTiO3+0.4SrTiO3 → Ba0.6Sr0.4TiO3 takes place, and this reaction is suggested to have a self-pinning effect on the grain growth, which in turn explains why this powder has a large kinetic window. Notably, SPS offers a unique opportunity to more preciously investigate and monitor the sintering kinetics of nano-powders, and it allows preparation of ceramics with tailored microstructures.The dielectric properties of selected samples of (Ba, Sr)TiO3 ceramics have been studied. The results are correlated with the microstructural features of these samples, e.g. to the grain sizes present in the compacts. The ceramic with nano-sized microstructure exhibits a diffuse transition in permittivity and reduced dielectric losses in the vicinity of the Curie temperature, whereas the more coarse-grained compacts exhibit normal dielectric properties in the ferroelectric region.The morphology evolution, with increasing sintering temperature, of bismuth layer-structured ferroelectric ceramics such as Bi4Ti3O12 (BIT) and CaBi2Nb2O9 (CBNO) was investigated. The subsequent isothermal sintering experiments revealed that the nano-sized particles of the BIT precursor powder grew into elongated plate-like grains within a few minutes, via a dynamic ripening mechanism.A new processing strategy for obtaining highly textured ceramics is described. It is based on a directional dynamic ripening mechanism induced by superplastic deformation. The new strategy makes it possible to produce a textured microstructure within minutes, and it allows production of textured ferroelectric ceramics with tailored morphology and improved physical properties.The ferroelectric, dielectric, and piezoelectric properties of the textured bismuth layer-structured ferroelectric ceramics have been studied, and it was revealed that all textured samples exhibited anisotropic properties and improved performance. The highly textured Bi4Ti3O12 ceramic exhibited ferroelectric properties equal to or better than those of corresponding single crystals, and much better than those previously reported for grain-orientated Bi4Ti3O12 ceramics. Textured CaBi2Nb2O9 ceramics exhibited a very high Curie temperature, d33-values nearly three times larger than those of conventionally sintered materials, and a high thermal depoling temperature indicating that it is a very promising material for high-temperature piezoelectric applications.

Three kinds of standard specimens, including low-alloy steels (Japanese iron and steel CRM), glass from NIST and Chinese geological reference materials were analyzed by wavelength dispersive X-ray fluorescence spectrometry as unknown samples. The fundamental parameter method was used to correct the matrix effect and different specimens including pure element specimens and type specimens were employed as calibration samples. The quantitative results were compared in order to study the influence of calibration samples on the accuracy of quantitative results. The study showed that the fundamental parameter method could correct the matrix effects very well and relatively accurate quantitative results could be obtained, corrected by simple specimens, in case of type calibration specimens’ absence.

A suspension stabilizer-coating technique was employed to prepare x mol% Yb 2 O 3 ( x = 1.0, 2.0, 3.0 and 4.0) and 1.0 mol% Y 2 O 3 co-doped ZrO 2 powder. A systematic study was conducted on the sintering behaviour, phase assemblage, microstructural development and mechanical properties of Yb 2 O 3 and Y 2 O 3 co-doped zirconia ceramics. Fully dense ZrO 2 ceramics were obtained by means of pressureless sintering in air for 1 h at 1450 °C. The phase composition of the ceramics could be controlled by tuning the Yb 2 O 3 content and the sintering parameters. Polycrystalline tetragonal ZrO 2 (TZP) and fully stabilised cubic ZrO 2 (FSZ) were achieved in the 1.0 mol% Y 2 O 3 stabilised ceramic, co-doped with 1.0 mol% Yb 2 O 3 and 4.0 mol% Yb 2 O 3 , respectively. The amount of stabilizer needed to form cubic ZrO 2 phase in the Yb 2 O 3 and Y 2 O 3 co-doped ZrO 2 ceramics was lower than that of single phase Y 2 O 3 -doped materials. The indentation fracture toughness could be tailored up to 8.5 MPa m 1/2 in combination with a hardness of 12 GPa by sintering a 1.0 mol% Yb 2 O 3 and 1.0 mol% Y 2 O 3 ceramic at 1450 °C for 1 h.

Theoretical equations to calculate fluorescence intensity enhanced by scattering effects for coating samples were developed based on fundamental parameter models. The secondary enhancement by scattering radiation from the same layer or between layer and substrate and the primary fluorescence that was scattered into the direction of detector by atoms in layer and substrate were included in calculations. The contributions of different scattering effects to fluorescence intensity were calculated for a hypothetical Zn coating on infinite Fe substrate sample. The results show that the contributions of scattering effects to fluorescence intensity are related to the thickness of coating and are up to several percents of primary fluorescence intensity.

The phase assembly of 1.0–5.0 mol% Nd 2 O 3 -doped ZrO 2 sintered at 1400 °C revealed that the tetragonal ZrO 2 phase could not be completely stabilised. Co-stabilising of 0.5–2.5 mol% Nd 2 O 3 with 0.5–1.0 mol% Y 2 O 3 , however, allowed the preparation of fully dense (Nd,Y)-TZP ceramics by pressureless sintering in air at 1450 °C. The mixed stabiliser monoclinic zirconia nanopowder starting material was synthesized from a suspension of neodymium nitrate, yttrium nitrate and monoclinic zirconia powder in an alcohol/water mixture. A HV 30 hardness of 10 GPa combined with an excellent indentation toughness of 13 MPa m 1/2 could be achieved for the (1.0Nd,1.0Y)- and (1.5Nd,1.0Y)-TZP ceramics. The influence of the mixed stabiliser content on the phase stability and mechanical properties are investigated and discussed.

CeO2-doped ZrO2, (8 mol%) starting powder was sintered by means of spark plasma sintering (SPS) at 1300 degrees C without holding time. The stability of the tetragonal ZrO2 phase in the Ce-ZrO2 ceramic sintered under strongly reducing conditions was investigated. The SPS sample consisted of monoclinic and tetragonal ZrO2 phase, with a volume ratio of two to one, as well as a trace amount of a Zr-Ce-O cubic solid solution phase. In contrast, the same powder sintered by hot-pressing in nitrogen at 1300 and 1500 degrees C for 1h showed no tetragonal ZrO2. Microstructural observation of the SPS ceramic by SEM and TEM revealed grains with and without twins. The reason for the appearance of the tetragonal phase in the SPS sample sintered under strongly reducing conditions is discussed. (c) 2004 Elsevier Ltd. All rights reserved.

The contributions of scattering effects to the X-ray fluorescent intensities were calculated by considering the intensity of scattered primary fluorescence radiation that is scattered into the direction of detector, the secondary enhancement by coherent scattering radiation and incoherent scattering radiation for light matrix samples on the basis of the theoretical calculations. Relative intensities for nine different characteristic X-ray lines for the synthesized fused disks were calculated and compared with the measured relative intensities. It was found from this study that the contributions of scattering effects to the fluorescent intensities of analytes in fused disk samples are sizeable. Moreover, the magnitude of contribution of scattering effects increases with the increase of atomic number of analyte or/and the decrease of the content of the fluorescent element in the fused disk samples, which is about several percents of that excited by primary radiation, or even more than 10% for PbLβ1. The average relative error of the calculated relative intensities compared with the measured values is 0.93% after scattering effects was considered, while the average relative error of the values calculated by NRLXRF for the same lines is 2.75%. The calculated relative intensities after considering the scattering effects are more agreeable to the measured values. Therefore, more accurate results for fundamental parameter method are expected with the consideration of scattering effects, especially for light matrix samples.

The characteristics of Eu-stabilized α-sialon ceramics derived from self-propagating high-temperature synthesis (SHS) Eu α-sialon powders without and with the addition of Y 2 O 3 are investigated. The results showed that the amount of α-sialon phase formed in sintered Eu α-sialon composition was much less than that in SHS-ed powder when the composition was hot-pressed at 1800 °C for 1 h, while the transformation of α-sialon to β-sialon phase did occur at the same time, which could be attributed to the metastability of SHS-ed powder because of the high heating and cooling rate during the SHS process and the reduction of Eu 3+ to Eu 2+ under the reduction conditions during hot pressing. By addition of Y 2 O 3 into SHS-ed Eu α-sialon powder, thus to form (Y,Eu) α-sialon phase in the sintered sample, the stability of α-sialon phase was improved, as the ratio of α-sialon to α-sialon was increased from 70 wt.% in SHS-ed powder to 83 wt.% in the sintered product by 50 mol% of Y 2 O 3 added into SHS-ed powder.

Different ratios of Ce to Y were selected to stabilize (Ce,Y) α-sialon during self-propagating high-temperature synthesis (SHS). The phase assemblages were then studied for both SHS-ed (Ce,Y) α-sialon powders and sintered ceramics. The results showed that the amount of α-sialon phase increased as a main crystalline phase in SHS-ed powders when 20 at.% of Ce was replaced by Y in the composition, and further increase in the substitution of Y for Ce did not obviously increase the α-sialon content, whereas β-sialon was the major phase in the SHS-ed powders without the introduction of Y in the composition. The transformation of α-sialon to β-sialon did occur when the SHS-ed powders were hot-pressed for the compositions without Y and substitution of Y for Ce less than 40 at.%. The 50 at.% replacement of Ce by Y was enough to stabilize (Ce,Y) α-sialon structure as the (Ce,Y) α-sialon phase was kept in the sample with similar amount to that in the SHS-ed powders.