The Role of Al in Cross‐Linking of Alkali‐Activated Slag Cements

The structural development of a calcium (sodium) aluminosilicate hydrate (C–(N‐)A–S–H) gel system, obtained through the reaction of sodium metasilicate and ground granulated blast furnace slag, is assessed by high‐resolution ²⁹Si and ²⁷Al MAS NMR spectroscopy during the first 2 yr after mixing. The cements formed primarily consist of C–(N‐)A–S–H gels, with hydrotalcite and disordered alkali aluminosilicate gels also identified in the solid product assemblages. Deconvolution of the ²⁷Al MAS NMR spectra enables the identification of three distinct tetrahedral Al sites, consistent with the ²⁹Si MAS NMR data, where Q³(1Al), Q⁴(3Al), and Q⁴(4Al) silicate sites are identified. These results suggest significant levels of cross‐linking in the C–(N‐)A–S–H gel and the presence of an additional highly polymerized aluminosilicate product. The mean chain length, extent of cross‐linking, and Al/Si ratio of the C–(N‐)A–S–H gel decrease slightly over time. The de‐cross‐linking effect is explained by the key role of Al in mixed cross‐linked/non‐cross‐linked C–(N‐)A–S–H gels, because the cross‐linked components have much lower Al‐binding capacities than the noncross‐linked components. These results show that the aluminosilicate chain lengths and chemical compositions of the fundamental structural components in C–(N‐)A–S–H gels vary in a way that is not immediately evident from the overall bulk chemistry.     

Effect of BBS‐Based Frit on the Low Temperature Sintering and Electrical Properties of KNN Lead‐Free Piezoceramics

Using BaO–B₂O₃–SiO₂ (BBS)‐based frit as sintering aid, the K_0.49Na_0.51NbO₃ (KNN) + x wt% BBS (x = 1.0, 1.5, 2.0 and 2.5) lead‐free piezoelectric ceramics were successfully fabricated by solid‐state reaction method under low‐sintering temperature of 1000°C. The effect of BBS frit doping amount on the structure and electrical properties of the ceramics was investigated. The KNN ceramics with 1.5 wt% BBS frit showed optimal properties as follows: piezoelectric constant d₃₃ = 108 pC/N, planar electromechanical coupling coefficient k_p = 41%, mechanical quality factor Q_m = 225, relative dielectric constant ε_r = 410, dielectric loss tanδ = 0.57% and Curie temperature T_c = 400°C. This ceramic sample should be a good lead‐free candidate for actuators or high temperature sensors application due to its ultra‐low tanδ, relatively high Q_m and T_c.     

Structure,Ferroelectric, Piezoelectric,and Ferromagnetic Properties of BiFeO3‐BaTiO3‐Bi0.5Na0.5TiO3 Lead‐Free Multiferroic Ceramics

Lead‐free multiferroic ceramics of BiFeO₃‐BaTiO₃‐Bi_0.5Na_0.5TiO₃ have been prepared by a conventional ceramic technique. The microstructure, multiferroic, and piezoelectric properties of the ceramics have been studied. The ceramics sintered at 1000°C for 2 h possess a pure perovskite structure and a morphotropic phase boundary of rhombohedral and tetragonal phases is formed at x = 0.02. After the addition of Bi_0.5Na_0.5TiO₃, two dielectric anomalies are observed at high temperatures (T_m ~ 510°C–570°C and T₂ ~ 720°C). The phase transition around T_m becomes wider gradually with increasing x. The ferroelectricity, piezoelectricity, and ferromagnetism of the ceramics are significantly improved after the addition of Bi_0.5Na_0.5TiO₃. High resistivity (~1.3 × 10⁹ Ω·cm), strong ferroelectricity (P_r = 27.4 μC/cm²), good piezoelectricity (d₃₃ =140 pC/N, k_p = 31.4%), and weak magnetic properties (M_r =0.19 emu/g) are observed.     

Low Temperature Sintering and Enhanced Piezoelectricity of Lead‐Free (Na0.52K0.4425Li0.0375)(Nb0.86Ta0.06Sb0.08)O3 Ceramics Prepared from Nano‐Powders

(Na_0.52K_0.4425Li_0.0375)(Nb_0.86Ta_0.06Sb_0.08)O₃ powders were synthesized via sol–gel and solid‐state reaction methods as a raw material for the preparation of the ceramics. Dependence of piezoelectric properties and microstructure on sintering temperatures was investigated in this study. Sol–gel‐derived nano‐powders could be densified at a lower temperature of 940°C and exhibited excellent electrical properties after sintering at 1020°C (d₃₃ = 424 pC/N, d₃₃^* = 780 pm/V, k_p = 52.1%, and T_c = 265°C). The enhanced electric properties were most likely due to the coexistence of orthorhombic and tetragonal phase in the samples at room temperature, homogenous microstructure with fine grain and high density.     

Effect of Temperature on C3S and C3S + Nanosilica Hydration and C–S–H Structure

This study aimed to monitor the effect of temperature and the addition of nanosilica on the nanostructure of the C–S–H gel forming during tricalcium silicate (C₃S) hydration. Two types of paste were prepared from a synthesized T₁ C₃S. The first consisted of a blend of deionized water and C₃S at a water/solid ratio of 0.425. In the second, a 90 wt% C₃S + 10 wt% of nanosilica blend was mixed with water at a water/solid ratio of 0.7. The pastes were stored in closed containers at 100% RH and 25°C, 40°C, or 65°C. The hydration reaction was detained after 1, 14, 28, or 62 d with acetone, and then pastes were studied by ²⁹Si magic angle spinning nuclear magnetic resonance (²⁹Si MAS NMR).The main conclusion was that adding nSA expedites C₃S hydration at any age or temperature and modifies the structure of the C–S–H gel formed, two types of C–S–H gel appear. At 25°C and 40°C, more orderly, longer chain gels are initially (1 d) obtained as a result of the pozzolanic reaction between nSA and portlandite (CH) (C–S–H_II gel formation). Subsequently, ongoing C₃S hydration and the concomitant flow of dimers shorten the mean chain length in the gel.     

New Lead‐Free (1 − x)(K0.5Na0.5)NbO3–x(Bi0.5Na0.5)ZrO3 Ceramics with High Piezoelectricity

For enhancing the piezoelectric properties of ceramics (Bi_0.5Na_0.5)ZrO₃ (BNZ) was used to partially substitute (K_0.5Na_0.5)NbO₃ (KNN). The addition of BNZ changes the symmetry of KNN ceramics from orthorhombic to tetragonal, and finally to rhombohedral phase. A new phase boundary with both rhombohedral–orthorhombic and orthorhombic–tetragonal phase transitions near room temperature is identified for KNN–0.050BNZ ceramics, where optimum electrical properties were obtained: d₃₃ = 360 pC/N, k_p = 32.1%, ε_r = 1429, tanδ = 3.5%, and T_C = 329°C. The results indicated a new method for designing high‐performance lead‐free piezoelectric materials.     

Cross‐Linking of Polyesters Based on Fatty Acids

This study aims at obtaining cross‐linked polymeric materials of biomass origin. For this purpose, one‐pot polyesterification of methyl ricinoleate and methyl 12‐hydroxystearate using titanium isopropoxide as a catalyst is performed leading to polyesters known as estolides. The obtained estolides are successfully cross‐linked using dicumyl peroxide or a sulfur vulcanization system. The so‐formed bio‐based elastomers appear to exhibit promising properties. The latter are analyzed by mechanical tensile tests and thermal techniques (TGA, DSC, DMA) and show high thermal stability (T_5% = 205–318 °C), tailored physico‐mechanical properties (low glass transition temperature in the range from ?69 to ?54 °C), and good tensile strength (0.11–0.40 MPa). Networks prepared from high molecular weight estolides appear to be promising bio‐based elastomers. Practical Applications: The vegetable oil‐based estolides described in this contribution are new fully bio‐based precursors for further elastomers synthesis. The resulting estolide networks (obtained by peroxide or sulfur cross‐linking) exhibit tailored thermo‐mechanical properties.     

Synthesis and Crystal Structure of Na2Ba9Si20O50—An Intermediate Phase Along the Join Na2Si2O5‐BaSi2O5

Single crystals of Na₂Ba₉Si₂₀O₅₀ were obtained from solid state reactions performed along the join Na₂Si₂O₅‐BaSi₂O₅. The crystal structure has been determined from a data set collected at ambient temperatures and subsequently refined to a residual of R(|F|) = 0.0328 for 2211 independent reflections. The compound belongs to the group of phyllosilicates and adopts the monoclinic space group C2/m with the following lattice parameters: a = 39.111(3) Å, b = 7.6566(6) Å, c = 8.2055(6) Å, β = 97.319(6)°, V = 2437.2(3) Å³, Z = 2. Furthermore, weak one‐dimensional diffuse streaks running parallel to a* as well as a very small number of low intensity reflections at b*/3, indicating the presence of a superstructure, were observed. Basic buiding units are silicate layers parallel to (40‐1) which can be obtained from the condensation of single chains with a periodicity of four running along [010]. The sheets can be partitioned into two kinds of consecutive strips containing (i) a sequence of four‐ and eight‐membered rings and (ii) a four‐ring wide “zig‐zag shaped” unit consisting of exclusively six‐membered rings. The sodium and barium cations—distributed among six crystallographically independent positions—are sandwiched between subsequent layers and are linked to seven to nine nearest oxygen neighbors. The structure of Na₂Ba₉Si₂₀O₅₀ is closely related to that of K₂Ba₅Si₁₂O₃₀ and K₂Ba₇Si₁₆O₄₀, respectively. There are strong arguments that the previously claimed phase Na₄Ba₈Si₂₀O₅₀ is actually misinterpreted Na₂Ba₉Si₂₀O₅₀ and that the composition of the intermediate phase along the join Na₂Si₂O₅–BaSi₂O₅ is slightly different from that described in the literature.     

High Na‐ion conducting Na1+x[SnxGe2−x(PO4)3] glass‐ceramic electrolytes: Structural and electrochemical impedance studies

Na‐ion conducting Na_1+x[Sn_xGe_2?x(PO₄)₃] (x = 0, 0.25, 0.5, and 0.75 mol%) glass samples with NASICON‐type phase were synthesized by the melt quenching method and glass‐ceramics were formed by heat treating the precursor glasses at their crystallization temperatures. XRD traces exhibit formation of most stable crystalline phase NaGe₂(PO₄)₃ (ICSD‐164019) with trigonal structure. Structural illustration of sodium germanium phosphate [NaGe₂(PO₄)₃] displays that each germanium is surrounded by 6 oxygen atom showing octahedral symmetry (GeO₆) and phosphorous with 4 oxygen atoms showing tetrahedral symmetry (PO₄). The highest bulk Na⁺ ion conductivities and lowest activation energy for conduction were achieved to be 8.39 × 10^?05 S/cm and 0.52 eV for the optimum substitution levels (x = 0.5 mol%, Na_1.5[Sn_0.5Ge_1.5(PO₄)₃]) of tetrahedral Ge⁴⁺ ions by Sn⁴⁺ on Na–Ge–P network. CV studies of the best conducting Na_1.5[Sn_0.5Ge_1.5(PO₄)₃] glass‐ceramic electrolyte possesses a wide electrochemical window of 6 V. The structural and EIS studies of these glass‐ceramic electrolyte samples were monitored in light of the substitution of Ge by its larger homologue Sn.     

“Metakaolin‐Slag‐Clinker Blends.” The Role of Na+ or K+ as Alkaline Activators of Theses Ternary Blends

This article reports on research into the use of solid alkalis (Na₂CO₃ and K₂CO₃) as activators to obtain hybrid cement (cement whose hydration generates a mix of C–A–S–H and (N,C)–A–S–H gels) from a blend of 20% clínker + 40% blast furnace slag + 40% metakaolin. More specifically, the study aimed to determine the effect of activator dosage (5 and 8 wt%) and type of alkaline cation (Na⁺ or K⁺) on the 2‐ and 28‐d mechanical strength of the end materials. The findings showed that the highest mechanical strength values were obtained with 5% Na₂CO₃. According to the XRD, NMR, and SEM/EDX analyses conducted on the reaction products, the alkalinity and solubilized chemical species generated by adding 5% Na₂CO₃ to the system yielded a mix of (N,C)–A–S–H and C–A–S–H cementitious gels as the main reaction products. The secondary reaction products included metastable (3CaO·Al₂O₃·CaCO₃·11H₂O‐type) carboaluminates that evolved into the calcite or vaterite forms of calcium carbonate. When K₂CO₃ was used (instead of Na₂CO₃), a (3CaO·Al₂O₃·0.5Ca(OH)₂·0.5CaCO₃·11H₂O‐type) hemicarboaluminate also formed. The study also revealed that Na⁺ favors coagulation/precipitation more effectively than K⁺, generating gels with a wider range of Qⁿ species.     

Ultra‐low Sintering Temperature Microwave Dielectric Ceramics Based on Na2O‐MoO3 Binary System

The compounds in Na₂O‐MoO₃ system were prepared by the solid‐state reaction route. The phase composition, crystal structures, microstructures, and microwave dielectric properties of the compounds have been investigated. This series of compounds can be sintered well at ultra‐low temperatures of 505°C–660°C. The sintered samples exhibit good microwave dielectric properties, with the relative permittivities (ε_r) of 4.1–12.9, the Q × f values of 19900–62400 GHz, and the τ_f values of ?115 ppm/°C to ?57 ppm/°C. Among the eight compounds in this binary system, three kinds of single‐phase ceramics, namely Na₂MoO₄, Na₂Mo₂O₇ and Na₆Mo₁₁O₃₆ were formed. Furthermore, the relationship between the structure and the microwave dielectric properties in this system has been discussed. The average Na^I‐O and Mo^VI‐O bond valences have an influence on the sintering temperatures in Na₂O‐MoO₃ system. The large valence deviations of Na and Mo lead to a large temperature coefficient of resonant frequency. The X‐ray diffraction and backscattered electron image results show that Na₂MoO₄ doesn't react with Ag and Al at 660°C. Also, Na₂Mo₂O₇ has a chemical compatibility with Al at 575°C.     

XRD Analysis of the Role of Cesium in Sodium‐Based Geopolymer

The purpose of this work was to study the role of cesium in sodium‐based geopolymer and its thermal stability for nuclear waste management. A series of mixed sodium and cesium geopolymer samples (Na_1?x Cs _x )₂O·Al₂O₃·SiO₂·12H₂O (referred to as (Na_{1? x} Cs _x )‐GP, where x = 0, 0.08, 0.15, 0.42, 1) have been prepared. All geopolymer samples were heated at 1100°C for 24 h. Pollucite (CsAlSi₂O₆) and feldspathoid (CsAlSiO₄) were crystallized from Cs‐GP. Nepheline (NaAlSiO₄) and a small amount of crystallized silica were obtained from Na‐GP. The other geopolymers (Na_{1? x} Cs _x )‐GP (x = 0.08, 0.15, 0.42) led to pollucite and nepheline main phases. Amorphous silica phase was observed in all the geopolymer samples with various amounts. Phase quantification and scanning electron microscope revealed that higher Cs concentrations in Na‐GP tend to decrease the amorphous phase while improving pollucite and nepheline phase quantification. The amorphous geopolymers have also been studied by pair distribution function analysis. Tetrahedral chains formed by T–O bonding (with T = Si, Al) were shown to be more tighten around Cs⁺ than around Na⁺. It led to shorter Cs–T bond than Na–T bond matching the higher solvation property of Na⁺. Furthermore, thermal study analysis pointed out the fact that geopolymer samples (Na_{1? x} Cs _x )‐GP, can be considered as solid solutions.     

Ultra‐Wide Temperature Stable Dielectrics Based on Bi0.5Na0.5TiO3–NaNbO3 System

The microstructure, phase structure, ferroelectric, and dielectric properties of (1?x)Bi_0.5Na_0.5TiO₃‐xNaNbO₃ [(1?x)BNT‐xNN] ceramics conventionally sintered in the temperature range of 1080°C–1120°C were investigated as a candidate for capacitor dielectrics with wide temperature stability. Perovskite phase with no secondary impurity was observed by XRD measurement. With increasing NN content, (1?x)BNT‐xNN was found to gradually transform from ferroelectric (x = 0–0.05) to relaxor (x = 0.10–0.20) and then to paraelectric state (x = 0.25–0.35) at room temperature, indicated by P–I–E loops analysis, associated with greatly enhanced dielectric temperature stability. For the samples with x = 0.25–0.35, the temperature coefficient of capacitance (TCC) was found <11% in an ultra‐wide temperature range of ?60°C–400°C with moderate dielectric constant and low dielectric loss, promising for temperature stable capacitor applications.     

Structure,Electrical, and Optical Properties of (Na1/2Bi1/2)TiO3–1.5at.%Bi(Zn1/2Ti1/2)O3 Lead‐free Single Crystal Grown by a TSSG Technique

Lead‐free single crystal (Na_1/2Bi_1/2)TiO₃–1.5 at.%Bi(Zn_1/2Ti_1/2)O₃ (NBT–1.5BZT) with dimension of Φ35 mm × 12 mm was successfully grown by a top‐seeded solution growth technique. The average and local structure were studied by a combination of X‐ray diffraction and Raman spectroscopy. The electric and optical properties of <001>‐oriented single crystals were investigated systematically. Compared with pure NBT, the piezoelectric constant and transmission coefficient were both enhanced, that is, from 62 pC/N and ~60% to 121 pC/N and ~70%, respectively. Furthermore, domain structure observation suggested that the <110>‐oriented tetragonal ferroelastic domains in NBT were suppressed at room temperature with addition of BZT, which was responsible for the improved piezoelectric and optical properties of NBT–1.5BZT single crystal.     

Nanodomains in KNN‐Based Lead‐Free Piezoelectric ceramics: Origin of Strong Piezoelectric Properties

Excellent piezoelectric properties of d₃₃* = 768 pm/V and strain = 0.07% at 1 kV/mm, were obtained by lead‐free in (Na_0.52K_0.4425Li_0.0375)(Nb_0.86Ta_0.06Sb_0.08)O₃ ceramics. They displayed good temperature stability up to 200°C. Significantly enhanced piezoelectricity originated from nanodomains of width 20–30 nm, and the result was confirmed by transmission electron microscopy. The above‐mentioned nanodomains emerged because of low domain wall energy near polymorphic phase transition regions and insignificant differences in cell parameters between orthorhombic and tetragonal phases. The nanodomain configuration easily responded to an external electric field, leading to high electric field‐induced strain.     

Properties and structures of nonstoichiometric (K,Na)NbO3‐based lead‐free ceramics

The 0.968[(K_0.48Na_0.52)]Nb_0.95+xSb_0.05O₃–0.032(Bi_0.5Na_0.5)ZrO₃ [KNN_xS–BNZ] lead‐free ceramics with nonstoichiometric niobium ion were fabricated via conventional solid‐state sintering technique and their piezoelectric, dielectric and ferroelectric properties were investigated. When x = 0.010, enhanced piezoelectric properties (d₃₃ ≈ 421 pC/N and k_p ≈ 0.47) were obtained due to the construction of rhombohendral—tetragonal phase boundary near room temperature. The KNN_xS–BNZ ceramics possesses enhanced Curie temperature (T_c) with improved piezoelectric constant. A large d₃₃ of ~421 pC/N and a high T_c ~256°C can be simultaneously induced in the ceramics with x = 0.010. Especially, good thermal stability was observed in a broad temperature range. The results indicated that our work could benefit development of KNN‐based ceramics and widen their application range.     

A single‐phase full‐color emitting phosphor Na3Sc2(PO4)3:Eu2+/Tb3+/Mn2+ with near‐zero thermal quenching and high quantum yield for near‐UV converted warm w‐LEDs

A single‐phase full‐color emitting phosphor Na₃Sc₂(PO₄)₃:Eu²⁺/Tb³⁺/Mn²⁺ has been synthesized by high‐temperature solid‐state method. The crystal structure is measured by X‐ray diffraction. The emission can be tuned from blue to green/red/white through reasonable adjustment of doping ratio among Eu²⁺/Tb³⁺/Mn²⁺ ions. The photoluminescence, energy‐transfer efficiency and concentration quenching mechanisms in Eu²⁺‐Tb³⁺/Eu²⁺‐Mn²⁺ co‐doped samples were studied in detail. All as‐obtained samples show high quantum yield and robust resistance to thermal quenching at evaluated temperature from 30 to 200°C. Notably, the wide‐gamut emission covering the full visible range of Na₃Sc₂(PO₄)₃:Eu²⁺/Tb³⁺/Mn²⁺ gives an outstanding thermal quenching behavior near‐zero thermal quenching at 150°C/less than 20% emission intensity loss at 200°C, and high quantum yield‐66.0% at 150°C/56.9% at 200°C. Moreover, the chromaticity coordinates of Na₃Sc₂(PO₄)₃:Eu²⁺/Tb³⁺/Mn²⁺ keep stable through the whole evaluated temperature range. Finally, near‐UV w‐LED devices were fabricated, the white LED device (CCT = 4740.4 K, Ra = 80.9) indicates that Na₃Sc₂(PO₄)₃:Eu²⁺/Tb³⁺/Mn²⁺ may be a promising candidate for phosphor‐converted near‐UV w‐LEDs.     

Use of glass waste as an activator in the preparation of alkali-activated slag. Mechanical strength and paste characterisation

The alkaline activation of aluminosilicates yields alkaline cements, eco-efficient alternatives to ordinary Portland cements. Alkaline cements and concretes exhibit highest strength and longest durability when activated with a solution of alkaline silicate hydrates (waterglass). To obtain these alkaline silicates, however, an aqueous solution of the proper proportion of carbonate and silica salts must be heated to temperatures of around 1300 °C. The present paper explores the feasibility of using urban and industrial glass waste as a potential alkaline activator for blast furnace slag (AAS).AAS pastes were prepared with three activators: waterglass, a NaOH/Na₂CO₃ mix and the solutions resulting from dissolving glass waste in NaOH/Na₂CO₃. Mechanical, mineralogical (XRD, FTIR) and microstructural (porosimetry, NMR and SEM/EDX) trials were conducted to characterise the pastes obtained.The findings proved the feasibility of using glass waste to alkali activate slag. Treating glass waste with NaOH/Na₂CO₃ (pH = 13.6) favours the partial dissolution of the Si in the glass into its most reactive monomeric form.The solutions resulting from the treatment of glass waste act as alkaline activators, partially dissolving vitreous blast furnace slag. The composition and microstructure of the reaction products identified in the two types of paste were similar. Strength and microstructural development in the pastes activated with glass waste were also comparable to the parameters observed in AAS pastes prepared with conventional activators.     

Temperature Stability of Lead‐Free Niobate Piezoceramics with Engineered Morphotropic Phase Boundary

The temperature dependence of piezoelectric properties (direct piezoelectric coefficient d₃₃, converse piezoelectric coefficient d₃₃(E = 0), strain S and electromechanical coupling coefficient k_p) for two niobate‐based lead‐free piezoceramics have been contrasted. 0.92(Na_0.5K_0.5)NbO₃–0.02(Bi_1/2Li_1/2)TiO₃–0.06BaZrO₃ (6BZ/2BLT/92NKN) has a morphotropic phase boundary (MPB) between rhombohedral and tetragonal at room temperature and 0.92(Na_0.5K_0.5)NbO₃–0.03(Bi_1/2Li_1/2)TiO₃–0.05BaZrO₃ (5BZ/3BLT/92NKN) features an MPB engineered to be located below room temperature. At 30°C, d₃₃, d₃₃(E = 0), S (at 2 kV/mm), and k_p are 252 pC/N, 230 pm/V, 0.069%, 0.51 for 5BZ/3BLT/92NKN; and 348 pC/N, 380 pm/V, 0.106%, 0.57 for 6BZ/2BLT/92NKN, respectively. With increasing temperature, the piezoelectric properties decrease. At 200°C, d₃₃, d₃₃(E = 0), S (at 2 kV/mm), and k_p are 170 pC/N, 160 pm/V, 0.059%, 0.36 for 5BZ/3BLT/92NKN; and 181 pC/N, 190 pm/V, 0.061%, 0.39 for 6BZ/2BLT/92NKN. It is found that the electromechanical coupling coefficient has a better temperature stability than the piezoelectric coefficient in the studied system due to a large temperature‐dependent compliance change. The results demonstrate that engineering an MPB is highly effective in tailoring temperature stability of piezoceramics.