Isotropic sintering shrinkage of 3D glass-ceramic nanolattices:backbone preforming and mechanical enhancement

There is a perpetual pursuit for free-form glasses and ceramics featuring outstanding mechanical properties as well as chemical and thermal resistance.It is a promising idea to shape inorganic materials in three-dimensional(3D)forms to reduce their weight while maintaining high mechanical properties.A popular strategy for the preparation of 3D inorganic materials is to mold the organic–inorganic hybrid photoresists into 3D micro-and nano-structures and remove the organic components by subsequent sintering.However,due to the discrete arrangement of inorganic components in the organic-inorganic hybrid photoresists,it remains a huge challenge to attain isotropic shrinkage during sintering.Herein,we demonstrate the isotropic sintering shrinkage by forming the consecutive–Si–O–Si–O–Zr–O–inorganic backbone in photoresists and fabricating 3D glass–ceramic nanolattices with enhanced mechanical properties.The femtosecond(fs)laser is used in two-photon polymerization(TPP)to fabricate 3D green body structures.After subsequent sintering at 1000℃,high-quality 3D glass–ceramic microstructures can be obtained with perfectly intact and smooth morphology.In-suit compression experiments and finite-element simulations reveal that octahedral-truss(oct-truss)lattices possess remarkable adeptness in bearing stress concentration and maintain the structural integrity to resist rod bending,indicating that this structure is a candidate for preparing lightweight and high stiffness glass–ceramic nanolattices.3D printing of such glasses and ceramics has significant implications in a number of industrial applications,including metamaterials,microelectromechanical systems,photonic crystals,and damage-tolerant lightweight materials.

Preparation, Crystallization and Mechanical Properties of Potassium Aluminosilicate Glass-ceramics

In this study,transparent K_(2)O-Al_(2)O_(3)-SiO_(2)(KAS)glass-ceramics with leucite as the main crystalline phase were prepared by melting-quench method and two-step heat treatment.The effects of SiO_(2)/Al_(2)O_(3) ratio and heat treatment on crystallization and mechanical properties were studied.The crystallization kinetics and X-Ray Diffraction(XRD)results showed that SiO_(2)/Al_(2)O_(3) ratio and heat treatment system had a direct impact on the crystallization behavior of potassium aluminosilicate glass-ceramics.When heat-treated at 680℃/2 h and 780℃/1 h,cracks generated on the surface of the sample with the addition of SiO_(2)/Al_(2)O_(3)=4.8(in mol)due to the huge difference in the coefficient of thermal expansion between glass matrix and surface.When the addition of SiO_(2)/Al_(2)O_(3)(in mol)was 4,the sample with leucite as the main crystalline phase showed an excellent fracture toughness(1.46 MPa·m^(0.5))after the heat treatment of 680℃/2 h and 780℃/5 h.And there was a phase transformation from kaliophilite to leucite.The crystalline phases of the sample heat-treated at 680℃/8 h and 780℃/1 h were leucite and kaliophilite,which resulted in the visible light transmittance of 63%and the fracture toughness of 0.91 MPa·m^(0.5).Furthermore,after the heat treatment of 680℃/2 h and 780℃/5 h,the main crystalline phase of the sample with SiO_(2)/Al_(2)O_(3)=3.2(in mol)was still kaliophilite.Because leucite only grows on the surface of the sample and is hard to grow inward,it is hard to achieve the bulk crystallization of leucite in the sample with SiO_(2)/Al_(2)O_(3)=3.2(in mol).

Glass-Ceramics with High Strength and High Transmittance Obtained by Multi-Factor Controlling

The presence of Li_(2)Si_(2)O_(5) and LiAlSi_(4)O_(10) could effectively improve the elastic modulus and transmittance of lithium disilicate(LD)glass-ceramics.Through synergistically modulation of the crystal content and grain size,we obtained high strength and high transmittance of LD glass-ceramics.The optimal sample had a high transmittance of 90.3%,the hardness was 7.72 GPa,the fracture toughness was 1.07 MPa·m^(1/2),and the elastic modulus was 103.1 GPa.

Achieving Narrowed Bandgaps and Blue-Light Excitability in Zero-Dimensional Hybrid Metal Halide Phosphors via Introducing Cation-Cation Bonding

Zero-dimensional(0D)hybrid metal halides,which consist of organic cations and isolated inorganic metal halide anions,have emerged as phosphors with efficient broadband emissions.However,these materials generally have too wide bandgaps and thus cannot be excited by blue light,which hinders their applications for efficient white light-emitting diodes(WLEDs).The key to achieving a blue-light-excitable 0D hybrid metal halide phosphor is to reduce the fundamental bandgap by rational chemical design.In this work,we report two designed hybrid copper(I)iodides,(Ph_(3)MeP)_(2)Cu_(4)I_(6)and(Cy_(3)MeP)_(2)Cu_(4)I_(6),as blue-light-excitable yellow phosphors with ultrabroadband emission.In these compounds,the[Cu_(4)I_(6)]^(2-)anion forms an I6 octahedron centered on a cationic Cu_(4)tetrahedron.The strong cation-cation bonding within the unique cationic Cu_(4)tetrahedra enables significantly lowered conduction band minimums and thus narrowed bandgaps,as compared to other reported hybrid copper(I)iodides.The ultrabroadband emission is attributed to the coexistence of free and self-trapped excitons.The WLED using the[Cu_(4)I_(6)]^(2-)anion-based single phosphor shows warm white light emission,with a high luminous efficiency of 65 Im W^(-1)and a high color rendering index of 88.This work provides strategies to design narrow-bandgap 0D hybrid metal halides and presents two first examples of blue-light-excitable 0D hybrid metal halide phosphors for efficient WLEDs.

Achieving broadband near-infrared luminescence in Cr^(3+)-Activated Y_(2)Mg_(2)Al_(2)Si_(2)O_(12)phosphors via multi-site occupancy

Cr^(3+)-activated near-infrared(NIR)phosphors are key for NIR phosphor-converted light emitting diodes(NIR pc-LED).While,the site occupancy of Cr^(3+)is one of the debates that have plagued researchers.Herein,Y2Mg2Al2-Si_(2)O1_(2)(YMAS)with multiple cationic sites is chosen as host of Cr^(3+)to synthesize YMAS:xCr^(3+)phosphors.In YMAS,Cr^(3+)ions occupy simultaneously Al/SiO4 tetrahedral,Mg/AlO6 octahedral,and Y/MgO8 dodecahedral sites which form three luminescent centers named as Cr1,Cr2,and Cr3,respectively.Cr1 and Cr2 relate to an intermediate crystal field,with transitions of^(2)E→^(4)A_(2)and^(4)T_(2)→^(4)A_(2)occurring simultaneously.As Cr^(3+)concentration increases,the^(4)T_(2)→^(4)A_(2)transition becomes more pronounced in Cr1 and Cr2,resulting in a red-shift and broadband emission.Cr3 consistently behaves a weak crystal field and exhibits the broad and long-wavelength emission.Wide-range NIR emission centering at 745 nm is realized in YMAS:0.03Cr^(3+)phosphor.This phosphor has high internal quantum efficiency(IQE?86%)and satisfying luminescence thermal stability(I423 K?70.2%).Using this phosphor,NIR pc-LEDs with 56.6 mW@320 mA optical output power is packaged and applied.Present study not only demonstrates the Cr^(3+)multi-site occupancy in a certain oxide but also provides a reliable approach via choosing a host with diverse cationic sites and local environments for Cr^(3+)to achieve broadband NIR phosphors.

Fabrication of YAG:Ce^(3+) and YAG:Ce^(3+),Sc^(3+) Phosphors by Spark Plasma Sintering Technique

In this study,a single-doped phosphors yttrium aluminum garnet(Y_(3)Al_(5)O_(12),YAG):Ce^(3+),single-doped YAG:Sc^(3+),and double-doped phosphors YAG:Ce^(3+),Sc^(3+) were prepared by spark plasma sintering(SPS)(lower than 1 200℃).The characteristics of synthesized phosphors were determined using scanning electron microscopy(SEM),X-ray diffraction(XRD),and fluorescence spectroscopy.During SPS,the lattice structure of YAG was maintained by the added Ce^(3+) and Sc^(3+).The emission wavelength of YAG:Ce^(3+) prepared from SPS(425-700 nm) was wider compared to that of YAG:Ce^(3+) prepared from high-temperature solid-state reaction(HSSR)(500-700 nm).The incorporation of low-dose Sc^(3+) in YAG:Ce^(3+) moved the emission peak towards the short wavelength.

Properties of Ultra-low Thermal Expansion LAS Transparent Glass-ceramics Prepared by Spodumene

The glass-ceramics were prepared with the spodumene mineral as the main raw material,and the effects of ZrO_(2)replacing TiO_(2)on the samples were systematically investigated.The results show that the substitution of ZrO_(2)for TiO_(2)is not conductive to precipitate𝛽β-quartz solid solution phase,but can improve the transparency and flexural strength of glass-ceramics.And the glass-ceramic with the highest visible light transmittance(87%)and flexural strength(231.80 MPa)exhibits an ultra-low thermal expansion of-0.028×10^(-7)K^(-1)in the region of 30-700℃.

Synthesis and Luminescence Improvement of CaAlSiN_(3) Phosphors Doped with Eu^(2+) and Mn^(2+) for White LEDs

Eu^(2+) and Mn^(2+) co-activated CaAlSiN_(3) red phosphors were produced using the solid-state reaction tech⁃nique in a N2 environment.Excitation spectra,emission spectra,and diffuse reflection spectra were used to study the luminescence characteristics,energy gap,and thermal stability in detail.CaAlSiN_(3)∶Eu^(2+) exhibits an extended emission band when stimulated with 450 nm blue light,which is caused by the 4f65d to 4f7 transition of Eu^(2+).Similar⁃ly,CaAlSiN_(3)∶Mn^(2+) displays a wide emission band centered at 628 nm,which results from Mn^(2+)’s transition from 4T1(4G) to 6A1(6S).When the ions of Mn^(2+)were combined into CaAlSiN_(3)∶Eu^(2+),the photoluminescence intensity of Eu^(2+ )was greatly boosted because there was energy transfer and co-emission between Mn^(2+) and Eu^(2+).Beyond that,CaAlSiN_(3)∶Eu^(2+),Mn^(2+) emerges with splendid thermostability and high quantum efficiency,the quenching temperature surpasses 300℃,and the internal quantum efficiency is determined to be around 84.9%.The white LED was pack⁃aged with a combination of CaAlSiN_(3)∶Eu^(2+),Mn^(2+),LuAG∶Ce3+ and a blue chip.At a warm white-light corresponding color temperature(3009 K) with CIE coordinates(0.4223,0.3748),the color rendering index Ra has reached 93.2.CaAlSiN_(3)∶Eu^(2+),Mn^(2+) would have great application potential as a red-emitting phosphor for white LEDs.

Preparation of Long-Lasting Phosphorescence (LLP) Glass-Ceramic Materials

Three kinds of glass-ceramics, i.e., Mn 2+ doped zinc borosilicate, Eu 2+, Dy 3+ co-doped strontium aluminoborate and Eu 2+, Nd 3+ co-doped calcium aluminoborate were prepared, whose phosphorescence emission band peaks at 525, 516 and 464 nm, respectively. In preparation of these glass-ceramics the base glasses were gained by heating the mixed starting materials at high temperature to get the transparent glasses; then those glasses were heat-treated and turned to opaque glass-ceramics. X-ray diffraction (XRD) shows that the crystallites are ZnSiO 4, SrAl 2O 4 and α-CaAl 2B 2O 7, respectively. It is a useful way to get new LLP materials by the method reported in this work that may be considered as “from glass to crystal”.

Crystallization kinetics and temperature dependence of energy storage properties of niobate glass-ceramics

Glass-ceramic materials of strontium barium niobate system were prepared through a melt-quenching method. The effects of crystallization temperature on the mierostructure, dielectric property, breakdown strength and energy storage density of barium strontium niobate glass-ceramics were studied. The crystallization mechanism of the glass-ceramics was discussed and should be one-dimensional interfacial growth. The results indicate that the breakdown strength remarkably increases with the increase of crystallization temperature. The glass-ceramic heat treated at 900 ℃ was found to possess optimal properties with breakdown strength of 1300 kV/cm and energy storage density of 2.8 J/cm3, which is promising dielectric materials for high energy storage density dielectrics.

YAG∶Ce Phosphors for WLED via Nano-Pesudoboehmite Sol-Gel Route

The sub-micron sized YAG ： Ce phosphors were synthesized via a modified sol-gel method by peptizing nano-pesudoboehmite particulate. It is found that YAG phase from the dried gel powders appears at 1000 ℃ then the pure YAG phase exists at a relatively lower sintering temperature of 1400 ℃. The smaller sizes of phosphors in the ranges of 1 - 3 μm are obtained due to the contribution of seeding effects of nano-sized alumina particles to strengthen each step of the processes. Both the excitation and emission spectra of photoluminescence of the phosphor obtained at 1400 ℃ meet well with the spectroscopic requirements of the WLED phosphors.

Investigations on Valence-Change Behaviors of Europium Ions in Eu-Doped Aluminate and Silicate Phosphors

Compounds of Sr3Al2O6 ： Eu, SrgAl14O25 ： Eu, and BaZnSiO4 ： Eu were synthesized by high-temperature solid state reactions. The doping Eu^3 ＋ ions were partially reduced to Eu^2＋ in Sr4Al14O25：Eu and BaZnSiOg：Eu prepared in an oxidizing atmosphere, N^2 ＋ O2. However, such an abnormal reduction process could not be performed in Sr3Al2O6：Eu, which was also prepared in an atmosphere of N^2 ＋ O2. Moreover, even though Sr3A1EO6：Eu was synthesized in a reducing condition CO, only part of the Eu^3 ＋ ions was reduced to Eu^2 ＋ . The existence of trivalent and divalent europium ions was confirmed by photoluminescent spectra. The different valence-change behaviors of europium ions in the hosts were attributed to the difference in host crystal structures. The higher the crystal structure stiffness, the easier the reduction process from Eu^3 ＋ to Eu^2 ＋ .

Preparation and luminescent properties of CaAl_2O_4:Eu^(3+),R^+(R=Li,Na,K) phosphors

CaAl2O4:Eu3+,R+(R=Li+,Na+,K+) red phosphors were synthesized by solid state reaction method.X-ray diffraction(XRD) and photoluminescence(PL) were employed to characterize their structural and luminescent properties.It was found that the optimal sintering temperature and sintering time were 1200 °C and 4 h,respectively.The optimal concentration of doped Eu3+ was 3 mol.%.Furthermore,under ultraviolet excitation with a wavelength of 254 nm,these samples showed red luminescence which were probably attributed to...

Separation of Red (Y_2O_3: Eu^(3+)), Blue (Sr,Ca,Ba)_(10)(PO_4)_6Cl_2: Eu^(2+) and Green (LaPO_4:Tb^(3+),Ce^(3+)) Rare Earth Phosphors by Liquid/Liquid Extraction

A novel process for separation of red （Y2O3： Eu^3＋）, blue （Sr, Ca, Ba）10（PO4）6Cl2： Eu^2＋ and green （LaPO4： Tb^3＋, Ce^3＋） fine tricolor phosphor powders was established. First, the green phosphor was extracted and separated from three phosphor mixtures in heptane/DMF（N, N-Dimethylformamide） system using stearylamine or laurylamine （DDA） as the cationic surfactant. Then, after being treated with 99.5% ethanol, the blue and red phosphors could be separated in Heptane/DMF system in presence of 1-octanesulfonic acid sodium salt as the anionic surfactant. Satisfactory separation results have been achieved through two steps extractions with their artificial mixtures. The grades and recovery of separated products reached respectively as follows： red product was 95.3% and 90.9%, blue product was 90.0% and 95.2%, and green product was 92.2% and 91.8%.

Effect of Yb^(3+) concentration on the structures and upconversion luminescence properties of Y_2O_3:Er^(3+) ultrafine phosphors

Y2O3：Er^3＋ ultrafine phosphors with a varying Yb^3＋ ion concentration were prepared by a urea homogeneous precipitation method. The results of XRD show that all the samples are of a pure cubic structure and the average crystallite sizes can be calculated as 45, 34, and 28 nm for Y2O3：Er^3＋ ultrafine phosphors with Yb^3＋ ion concentrations of 0, 10%, and 20%, respectively. The lattice constant and cell volume of the ultrafine phosphors decrease with enhancing Yb^3＋ ion concentration. The upconversion luminescence spectra of all the samples were studied under 980 nm laser excitation. The strong green and red upconversion emission were observed, and attributed to the ^2H11/2→^4I15/2, ^4S3/2 → ^4I15/2 and ^4F9/2 →^4I15/2 transitions of Er^3＋, respectively. The intensity of red emission increases with increasing Yb^3＋ ion concentration. The effect of Yb^3＋ ion concentration on the structures and upconversion luminescence mechanism were discussed.

Synthesis and Characterization of Cerium-Doped Lutetium Aluminum Garnet Phosphors by Nitrate-citrate Sol-Gel Combustion Process

Nanosized cerium-doped lutetium aluminum garnet （LuAG：Ce） phosphors were prepared by nitrate-citrate solgel combustion process using 1：1 ratio of the citrate：nitrate. The prepared LuAG：Ce phosphors were characterized by XRD, TEM, photoluminescence and radioluminescence spectra excited by UV and X-ray, respectively. The purified crystalline phase of LuAG：Ce was obtained at 900 ℃ by directly crystallizing from amorphous materials. The resultant Lu- AG：Ce phosphors were uniform and had good dispersivity with an average particle size of about 30 urn. Both photoluminescence and radioluminescence were well-known Ce^3＋ emissions located in the range of 470 -600 nm consisting of two emission bands because of the transition from the lowest 5d excited state （2D） to the 4f ground state of Ce^3＋, which matched well with the sensitivity curve of the Si-photodiode. There was a little red shift for the emission components from the UV-excited emission spectrum to the X-ray-excited emission spectrum. The fast scintillation decay component of 26 ns satisfies the requirements of fast scintillators.

Effect of fluxes on structure and luminescence properties of Y_3Al_5O_(12):Ce^(3+) phosphors

Ce3＋-activated yttrium aluminum garnet （YAG） was prepared by the solid-state reaction, in which H3BO3, LiF, NaF, KF and BaF2 were used as the fluxes. The effect of fluxes on optical properties of phosphors was studied in detail, especially the fluxes of alkali fluorides, which could enhance the emission intensity and change the wavelength of emission peaks. Among these YAG：Ce phosphors, the phosphor sintered with H3BO3 and NaF exhibited the strongest emission. The emission peaks of phosphors prepared with fluxes from LiF to KF were shifted to long wavelength. The effect of NaF concentration on the emission intensity of YAG：Ce was also investigated. The value of emission intensity reached the maximum when the concentration of NaF was 0.5%.

Influence of aluminium nitride as a foaming agent on the preparation of foam glass-ceramics from high-titanium blast furnace slag

To effectively reuse high-titanium blast furnace slag （TS）, foam glass-ceramics were successfully prepared by powder sintering at 1000℃. TS and waste glass were used as the main raw materials, aluminium nitride （AIN） as the foaming agent, and borax as the fluxing agent. The influence of the amount of A1N added （lwt%-5wt%） on the crystalline phases, microstructure, and properties of the produced foam glass-ceramics was studied. The results showed that the main crystal phases were perovskite, diopside, and augite. With increasing A1N content, a transformation from diopside to augite occurred and the crystallinity of the pyroxene phases slightly decreased. Initially, the aver- age pore size and porosity of the foam glass-ceramics increased and subsequently decreased; similarly, their bulk density and compressive strength decreased and subsequently increased. The optimal properties were obtained when the foam glass-ceramics were prepared by adding 4wt% AIN.

Synthesis and Luminescence Properties of Red Phosphors:Mn^(2+) Doped MgSiO_3 and Mg_2SiO_4 Prepared by Sol-Gel Method

Sol-gel method was utilized to synthesize two different series of red silicate phosphors : MgSiO3 and Mg2SiO4 powder samples doped with Mn2+, conducted the investigation of red long-lasting phosphor: MgSiO3 : Eu2 + , Dy3+, Mn2+ . TGA curves of the gel precursor for two series depicted that the loss of residual organic groups and NO3 groups occurs below 450℃. According to the XRD patterns, the major diffraction peaks of the MgSiO3 and Mg2SiO4 series are consistent with a proto-enstatite structure (JCPDS No.11-0273) and a forsterite structure (JCPDS No.85-1364) respectively. With the excitation at 415 nm, the red emission band of Mn2+ ions is peaked at 661 nm for MgSiO3:1%(atom fraction) Mn2+ or 644 nm for MgiSiO4: 1 %(atom fraction) Mn2+ . Compared with Mg2SiO4:Mn2+ samples, MgSiO3:Mn2+ samples exhibit higher luminescence intensity and higher quenching concentration. In addition, the two series co-doped with Eu2+ , Dy3+ , Mn2+ were also prepared. Photo-luminescence and afterglow properties of the two co-doped series were analyzed, which show that MgSiO3: Eu2 + , Dy3+ , Mn2+ is more suitable for a red long-lasting phosphor.

Controlled Synthesis and Application of α-Al_2O_3 for Lu_3Al_5O_(12): Ce^(3+) Green Spherical Phosphors

Al2O3 powders with different morphologies,namely fibrous,sheet-like,and spherical,were prepared by the hydrothermal-thermolysis method.Subsequently,polycrystalline,transparent cerium doped lutetium aluminum garnet（Lu3Al5O（12）：Ce^3＋）green phosphors were synthesized by high temperature solidstate method using commercial lutetium（III）oxide,cerium（III）oxide,and as-prepared Al2O3 powders with different morphologies.The phases,morphologies,and photoluminescent properties of the prepared phosphors were investigated by X-ray diffraction（XRD）,scanning electron microscopy（SEM）,and photoluminescence spectroscopy（PL）.Moreover,the influences of the morphologies ofα-Al2O3 on the types of crystal structure,morphologies,and photoluminescent properties of LuAG：Ce^3＋green phosphors were investigated.The results indicated that the morphologies and particle sizes of theα-Al2O3 powders could be controlled by the additives and parameters.Notably,the sphericalα-Al2O3 powders with good dispersibility were found to be the excellent base materials of LuAG：Ce^3＋green phosphors for white light emitting diodes.