Quantitative investigation on the preferential flow induced by desiccation cracks (PF-DC) remains a great challenge due to the soil shrinking-swelling behavior. This work presents a series of comparative numerical studies to investigate the accuracy and substitutability of different models in simulating the water flux, hydrological response and crack evolution induced by PF-DC. As a comparative study, an effective dynamic dual-permeability model (DDPM) we recently developed and validated was regarded as a benchmark model. Three numerical experiments were conducted to (i) compare the difference among the single-domain model (SDM), rigid dual-permeability model (RDPM) and DDPM; (ii) test the sensitivity of the DDPM to the shrinking-swelling parameters; (iii) test the rationality of a “lighter” dynamic DPM (LDPM) only considering the proportion changes of each domain while neglecting the variation of hydraulic properties. The results showed that compared to the DDPM, the SDM overestimated the water content under low-rainfall intensity while underestimating the water content under high-intensity rainfall and failed to capture the early increase of water content in deep soils induced by PF-DC. The RDPM greatly overestimated the total water content and water storage capacity of the crack domain, which was not suggested to be used in the surface runoff or flood forecast. The DDPM is overall not sensitive to the shrinking-swelling parameters, indicative of relatively loose accuracy requirements in measuring the soil shrinking-swelling parameters. The LDPM can be a tentative alternative option for the DDPM, but it is better not to use it to evaluate the surface runoff or use it under long-term extreme drought. In conclusion, the prediction errors without considering crack evolution and variation of hydraulic properties of each domain (RDPM) are the highest, then followed by the only considering crack evolution (LDPM) and uncertainties of shrinking-swelling parameters.

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Preferential flow induced by desiccation cracks (PF-DC) has been proven to be an important hydrological effect that could cause various geotechnical engineering and ecological environment problems. Investigation on the PF-DC remains a great challenge due to the soil shrinking–swelling behavior. This work presents an experimental and numerical study of the PF-DC considering the dynamic changes of desiccation cracks. A soil column test was conducted under wetting–drying cycles to investigate the dynamic changes of desiccation cracks and their hydrological response. The ratios between the crack area and soil matrix area (crack ratio), crack aperture and depth were measured. The soil water content, matrix suction and water drainage were monitored. A new dynamic dual-permeability preferential flow model (DPMDy) was developed, which includes physically consistent functions in describing the variation of both porosity and hydraulic conductivity in crack and matrix domains. Its performance was compared to the single-domain model (SDM) and rigid dual-permeability model (DPM) with fixed crack ratio and hydraulic conductivity. The experimental results showed that the maximum crack ratio and aperture decreased when the evaporation intensity was excessively raised. The self-closure phenomenon of cracks and increased surficial water content was observed during low-evaporation periods. The simulation results showed that the matrix evaporation modeled by the DPMDy is lower than that of the SDM and DPM, but its crack evaporation is the highest. Compared to the DPM, the DPMDy simulated a faster pressure head building-up process in the crack domain and higher water exchange rates from the crack to the matrix domain during rainfall. Using a fixed crack ratio in the DPM, whether it is the maximum or the average value from the experiment data, will overestimate the infiltration fluxes of PF-DC but underestimate its contribution to the matrix domain. In conclusion, the DPMDy better described the underlying physics involving crack evolution and hydrological response with respect to the SDM and DPM. Further improvement of the DPMDy should focus on the hysteresis effect of the soil water retention curve and soil deformation during wetting–drying cycles.@en

Phosphors with high quantum efficiency and thermal stability are greatly desired for lighting industries. Based on the design strategy of solid solution, a series of deep-blue-emitting phosphors (Sr_0.99-xBa_x)₂P₂O₇:0.02Eu²⁺ (SB_xPE x = 0–0.5) are developed. Upon excitation at 350 nm, the optimized SB_0.3PE phosphor shows a relatively narrow full width at half maximum (FWHM = 32.7 nm) peaking at 420 nm, which matches well with the plant absorption in blue region. Moreover, this phosphor exhibits obvious enhancement of internal quantum efficiency (IQE) (from 74% to 100%) and thermal stability (from 88% to 108% of peak intensity and from 99% to 124% of integrated area intensity at 150°C) compared with the pristine one. The white LED devices using SB_0.3PE as deep-blue-emitting component show good electronic properties, indicating that SB_0.3PE is promising to be used in plant growth lighting, white LEDs, and other photoelectric applications. Inorganic Materials; Materials Application; Optical Materials

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Terbium and europium co-doped Sr ₈ ZnY(PO ₄ ) ₇ phosphors are successfully prepared through a high temperature solid-state reaction (SSR). The crystal structure of the as-prepared samples was identified to be Sr ₈ ZnY(PO ₄ ) ₇ (SZYP) pure phase by an X-ray powder diffraction technique. Under near-ultraviolet light excitation (378 nm), the SZYP:Tb ³⁺ and SZYP:Eu ³⁺ phosphors show green and red emission peaking at 545 and 618 nm, respectively. Moreover, an effective energy transfer process from Tb ³⁺ to Eu ³⁺ could be verified by the concentration dependence of emission intensity and lifetime. The energy transfer mechanism between Tb ³⁺ and Eu ³⁺ is determined to be governed by dipole-dipole interactions. The internal quantum efficiency (IQE) is evaluated to be as high as about 91%. The temperature-dependent spectra indicate that the SZYP:Tb ³⁺ ,Eu ³⁺ phosphor shows a high thermal stability. Furthermore, the as-fabricated white LED devices exhibit an excellent correlated color temperature (CCT) of 3223 K, a color rendering index (R _a ) of 85.8 and a luminance efficiency of 37.4 lm W ^-1 . All results imply that the SZYP:Tb ³⁺ ,Eu ³⁺ phosphors have a great potential for application in white LEDs.

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For plant-growth lighting, novel deep-red emission phosphors with high brightness were obtained by co-doping Ti⁴⁺ and Mn⁴⁺ into a Ca₁₄Al₁₀Zn₆O₃₅ substrate through a conventional solid-state reaction strategy. The nominal Ca_14-(x+y)/2Al_10-x-yZn₆O₃₅:xTi⁴⁺,yMn⁴⁺ (CAZO:Ti⁴⁺,Mn⁴⁺) phosphors could be excited by both near-ultraviolet (NUV) and blue-light-emitting diode (LED) chips efficiently and exhibited a strong deep-red emission band ranging from 650 nm to 750 nm, which should be the result of the ²E → ⁴A₂ transition inside the [MnO₆]^8- octahedral. Multiple energy transfer from Ti⁴⁺ to Mn⁴⁺ was detected in this CAZO; whereby Ti⁴⁺ and Mn⁴⁺ phosphors were verified to be a result of the dipole-dipole interaction under excitation at 270 nm. LED plant-growth lights were fabricated using the as-prepared nominal Ca_13.825Al_9.65Zn₆O₃₅:0.15Mn⁴⁺,0.2Ti⁴⁺,0.005H₃BO₃ (CAZO:Mn⁴⁺,Ti⁴⁺,H₃BO₃) phosphors pumped by a 460 nm blue-chip; this luminaire could be used to greatly promote the cultivation of succulent plants. Combined with the attractive thermal stability as well as high quantum efficiency (QE) of this phosphor, it was demonstrated that these novel phosphors may be candidate deep-red luminescent materials for LED plant lighting.

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Phosphor converted white light-emitting diodes (pc-WLEDs) are an alternative choice for general lighting due to their superior features such as high efficiency, durability and reliability. However, most pc-WLEDs in the market suffer from problems resulting from the lack of red emission, which can be resolved by adding red-emitting phosphors. The currently dominant red-emitting phosphors are Eu²⁺-doped nitrides, but the requirement of elevated temperature during synthesis makes them costly, and moreover the over broad emission may result in loss of lumen efficiency. Recently, transition metal Mn⁴⁺ doped materials showing very narrow red emission have attracted tremendous interest for compositions based on abundant resources and mild production processes, resulting in a highly efficient way to obtain phosphors with favorable luminescence properties. In this work, we describe the recent progress on transition metal Mn⁴⁺-doped inorganic luminescent materials, including oxides (subdivision into alkaline-earth germanates, arsenates, aluminates, titanates, pyrosilicates, phosphates, zirconates, gallates, simple oxides and others), fluorides and nitrides. More specifically, the review focuses on Mn⁴⁺ activated red-emitting phosphors that can be effectively excited by NUV and blue LED chips. The excitation and emission spectra as well as the preparation process of some representative phosphors are given and discussed. Meanwhile, the merits and drawbacks of several kinds of matrix materials in applications for white LEDs, as well as some problems, development trends and application prospects in this field of Mn⁴⁺ doped phosphors are summarized.

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