Defect engineering on phase structure and temperature stability of KNN‐based ceramics sintered in different atmospheres

Lead‐free MnO‐doped 0.955K_0.5Na_0.5NbO₃‐0.045Bi_0.5Na_0.5ZrO₃ (Abbreviated as KNN‐0.045BNZ) ceramics have been prepared by the conventional solid‐state sintering method in reducing atmosphere ( = 1 × 10^?10 atm) and air. For ceramics sintered in reducing atmosphere, only Mn²⁺ ions exist in ceramics who preferentially occupy the cation vacancies in A‐site at x = 0.2‐0.4, whereas Mn²⁺ ions substitute for Zr⁴⁺ ions in B‐site to form defects () at x > 0.4. For ceramics sintered in air, mixed Mn²⁺, Mn³⁺, and Mn⁴⁺ ions coexist here. The Mn²⁺ ions preferentially occupy the cation vacancies in A‐site at x = 0.2‐0.4 and then Mn²⁺ ions substitute for Zr⁴⁺ ions in B‐site at x > 0.4. Meanwhile, the Mn³⁺ ions and Mn⁴⁺ ions substitute for Nb⁵⁺ ions in B‐site to form defects () at x = 0.2‐0.8. The (, , and ) dipolar defects show a positive dipolar defect contribution (DDC) to the , whereas the dipolar defects () show a negative DDC to the . The dipolar defects ( ‐ and ) can help improve the temperature stability of . The 0.4% MnO‐doped KNN‐0.045BNZ ceramics sintered in reducing atmosphere show excellent piezoelectric constant d₃₃ = 300 pC/N and 0.2% MnO‐doped KNN‐0.045BNZ ceramics sintered in air possess optimal piezoelectric constant d₃₃ = 290 pC/N.     

Optical Evaluation of In Situ Crack Propagation by Using Mechanoluminescence of SrAl2O4:Eu2+, Dy3+

New theoretical solutions involving conventional crack propagation from static to dynamic fracture in terms of mechanoluminescence (ML) and the experimental techniques to trace the in situ crack and its instantaneous stress intensity factor (SIF) have been suggested in SrAl₂O₄:Eu²⁺, Dy³⁺ (SAO). The direct optical method to determine the moving crack tip on behalf of ML was verified by indirect crack mouth opening displacement (CMOD). The mode I SIF calculated from the instantaneous cumulative ML fringes showed proper agreement with the SIFs and acquired from conventional ASTM E‐399 measurements under quasidynamic condition. The magnitude and shape of the theoretically predicted crack tip stress field was in accordance with the experimental in situ ML evidence while determining the quasidynamic SIF from the cumulative ML intensity. Therefore, the use of ML technology could be one of the possible substitutive and substantial alternatives for structural health monitoring systems due to its simplicity but effectiveness in detecting arrested or propagating crack tips and in assessing the instantaneous structural integrity by means of the ML fracture parameters.     

Quantitative analyses of electric field–induced phase transition in (Na,K)0.5Bi0.5TiO3:Eu ceramics by photoluminescence

Most reported results about phase transition probed by the photoluminescence (PL) spectra of Eu³⁺ ions are qualitative, but the quantitative analyses of phase transition were presented in this work. We fabricated (Na_0.8, K_0.2)_0.5Bi_0.497Eu_0.003TiO₃ (NKBT20:Eu) ferroelectric ceramics and investigated the phase structures and the PL spectra of NKBT20:Eu ceramics before and after poling at different electric fields. The PL spectra indicate a phase transition from tetragonal phase (T phase) to rhombohedral phase (R phase) within NKBT20:Eu ceramics after poling, consistent with the analyses by X-ray diffraction (XRD). Moreover, the emission intensity ratios of the “hypersensitive” transition to the magnetic dipole transition could be used to calculate the fractions of the phase transition quantitatively, which were further confirmed by XRD Rietveld refinements. This study provides a different perspective to investigate the phase transition induced by electric field for NKBT20:Eu ceramics, qualitatively and quantitatively, and the method is expected to be useful in more cases of phase analyses.     

Cationic effect of charge compensation on the sulfide capacity of aluminosilicate slags

The effect of CaO on the sulfide capacity of CaO‐Al₂O₃‐SiO₂ slags was studied from the viewpoint of the ionic structure of alumina in slag. The aluminum coordination number was analyzed using ²⁷Al 500‐MHz solid nuclear magnetic resonance spectroscopy and the results were compared with those of the sulfide capacity analysis. The sulfide capacity of slag, in the peralkaline region (), exhibited a linear relationship with respect to basicity () as excess free Ca²⁺ formed a 4‐coordinated aluminum unit structure (^[IV]Al; ) and stabilized the sulfide ions (). However, sulfide capacity in the peraluminous region () exhibited a nonlinear relationship with respect to basicity () owing to the structure of higher‐coordinated aluminum units (^[V]Al, ^[VI]Al; Al³⁺) and the relative lack of Ca²⁺. Therefore, the sulfide capacity of high Al₂O₃‐bearing slags strongly depended on the basicity () and stability of sulfide ions (), which depended on the competitive behavior of Ca²⁺ owing to the structural changes in Al₂O₃. The effect of the aluminum coordination number on the sulfide capacity was discussed in detail using an analysis of the slag structure and thermodynamics model.     

Composition‐induced structural transitions and enhanced strain response in nonstoichiometric NBT‐based ceramics

In this work, the nonstoichiometric 0.99Bi_0.505(Na_0.8K_0.2)_0.5‐xTiO₃‐0.01SrTiO₃ (BNKST(0.5‐x)) ceramics with x=0‐0.03 were synthesized by conventional solid‐state reaction method. The composition‐induced structural transitions were investigated by Raman spectra, dielectric analyses, and electrical measurements. It is found that the relaxor phase can be induced through the modulation of the (Na, K) content. The (Na, K) deficiency in BNKST(0.5‐x) ceramics favors a more disordered local structure and can result in the loss of long‐range ferroelectricity. The x=0.015 critical composition possesses relatively high positive strain S_pos of 0.42% and large signal piezoelectric constant d₃₃* of 479 pm V^?1 at 6 kV mm^?1, along with the good temperature (25‐120°C) and frequency (1‐20 Hz) stability. The recoverable large strain responses in nonstoichiometric ceramics can be attributed to the reversible relaxor‐ferroelectric phase transition, which is closely related to the complex defects (, , and ) and the local random fields. This work may be helpful for the exploration of high‐performance NBT‐based lead‐free materials by means of A‐site compositional modification.     

Decisive role of mixed‐valence structure in colossal dielectric constant of LaFeO3

The role of mixed‐valence structure in colossal dielectric constant (CDC) behavior has been investigated in LaFeO₃ ceramics by tuning the ratio of Fe²⁺/Fe³⁺ through substituting Al for Fe. The ratio of Fe²⁺/Fe³⁺ is decreased gradually from 1.0 to 0.0 by increasing the concentration of Al³⁺. Two clear‐cut correlations have been found: (i) the relationship between the CDC behavior and the ratio of Fe²⁺/Fe³⁺ follows an exponential function and (ii) the activation energy of the polaron relaxation is proportional to , where is the intrinsic dielectric constant. These findings underscore the role of the mixed‐valence structure in CDC behavior and suggest that adjusting the mixed‐valence structure through doping/alloying can be a promising strategy to achieve superior CDC behavior in transition‐metal oxides.     

Temperature stability and electrical properties of MnO‐doped KNN‐based ceramics sintered in reducing atmosphere

Lead‐free MnO‐doped 0.955K_0.5Na_0.5NbO₃‐0.045Bi_0.5Na_0.5ZrO₃ (abbreviate as KNN‐0.045BNZ) ceramics have been prepared by a conventional solid‐state sintering method in reducing atmosphere. The MnO addition can suppress the emergence of the liquid phase and improve the homogenization of grain size. All ceramics sintered in reducing atmosphere show a two‐phase coexistence zone composed of rhombohedral (R) and tetragonal (T) phase. MnO dopant results in the content increase in R phase and slight increase in Curie temperature T_C. For KNN‐0.045BNZ ceramics, Mn²⁺ ions preferentially occupy the cation vacancies in A‐site to decrease oxygen vacancy concentration for 0.2%‐0.4% MnO content, whereas Mn²⁺ ions substitute for Zr⁴⁺ ions in B‐site to form oxygen vacancies at x ≥ 0.5. The defect dipole is formed at the moderate concentration from 0.5 to 0.6, which can provide a preserve force to improve the temperature stability of piezoelectric properties for k_p and . The Mn0.4 ceramics show excellent electrical properties with quasistatic piezoelectric constant d₃₃ = 300 pC/N, electromechanical coupling coefficient k_p = 51.2%, high field piezoelectric constant  = 430 pm/V (at E_max = 25 kV/cm) and T_C = ~345°C, insulation resistivity ρ  =  6.13 × 10¹¹ Ωcm.     

Effect of the (Ba + Sr)/Ti ratio on the microwave‐tunable properties of Ba0.6Sr0.4TiO3 ceramics

The impact of the (Ba + Sr)/Ti (A/B) ratio on the microwave‐tunable characteristics of diffuse phase transition (DPT) ferroelectric Ba_0.6Sr_0.4TiO₃ (0.6‐BST) ceramics was investigated. The reduction in the lattice constant with increasing nonstoichiometry was attributed to introduced partial Schottky defects, i.e., and . The magnitude of the dielectric constant, ε′, at room temperature in the absence of an applied electric field was governed by the shift in the dielectric maximum temperature, T_m, because T_m was close to room temperature for the 0.6‐BST. The dielectric loss, tanδ, diminished as the ε′ decreased for 0.98≤A/B≤1.05, while the tanδ was much higher for A/B=0.95 having the greatest A‐site vacancy loading. The negatively charged and were mainly compensated by oxygen vacancies and likely partly compensated by holes, h^?, which contributed to the electrical conduction. The tunability, T, at 100 MHz was almost constant at 20%–25% for A/B≥1.00 despite the reduction of the ε′, whereas T decreased for A/B<1.00 to ca. 10% for A/B=0.95 having the greatest A‐site vacancy loading. The results implied that the for larger A/B values was more efficient in generating nucleation sites in the polar nanoregions (PNRs) than the for smaller A/B values, thereby providing greater dipole polarization. Consequently, the figure of merit, FOM, reached its maximum of 250 at A/B=0.9875, which was ca. 155% higher than that of the stoichiometric BST.     

Thermodynamic properties of Si(OH)4(g) based on combined experimental and quantum chemistry data

The volatility of silicon‐based ceramics in combustion environments is primarily controlled by the formation of gaseous Si(OH)₄. The heat capacities and entropies of this species at 298.15‐2100 K and P = 0.1 MPa have been studied with the B3LYP density functional theory for the 6‐311+G(d,p) basis set in different approximations: a harmonic oscillator, an anharmonic oscillator, and with corrections for hindered rotors. Experimentally based Gibbs energies of Si(OH)₄(g) at 424‐1661 K have been employed to evaluate the Gibbs energy of formation, , and the entropy, , of Si(OH)₄(g) at = 298.15 K and P = 0.1 MPa. We found that the QC and “experimental” values are very close for the harmonic and anharmonic oscillator approximations, but not for the “hindered rotor” approximation. This conclusion is also supported by calculations of the OH rotational energy for Si(OH)₄ molecule, where the potential barrier was found to exceed 12 kJ/mol. Finally, we recommend the thermodynamic properties of Si(OH)₄ in the ideal gas state at P = 0.1 MPa over the temperature range of 298‐2100 K.     

Theoretical Prediction and Experimental Validation of Enhancing the Piezoelectric Properties of (K,Na)NbO3 Modified by Li,Ta, and Sb According to the Linear Combination Rule

Lead‐free piezoelectric ceramics of (K_, Na)NbO₃ modified by Li, Ta, and Sb (KNN‐LTS) have been widely investigated recently. In this research, this optimized composition of KNN‐LTS ceramics near polymorphic phase transition is explored according to the linear combination rule (LCR) for the first time. Changing with the compositions monotonically, remanent polarization (P_r) decreased monotonically, whereas permittivity () increased similarly. The increase in either or P_r initially enhances piezoelectric coefficient d₃₃ before reducing it because d₃₃ can be improved by and P_r. The optimal composition of (Na_0.52K_0.4415Li_0.0385)(Nb_0.8735Ta_0.064Sb_0.0625)O₃, predicted by LCR, exhibits the excellent electric properties of d₃₃ = 359 pC/N, k_p = 42%, thus suggesting that the LCR effectively predicts the electric properties of the KNN‐LTS ceramics.     

Improving piezoelectric properties and temperature stability for KNN‐based ceramics sintered in a reducing atmosphere

Lead‐free 0.955K_0.5Na_0.5Nb_1‐zTa_zO₃‐0.045Bi_0.5Na_0.5ZrO₃+0.4%MnO ceramics (abbreviated as KNNTaz‐0.045BNZ+0.4Mn) were prepared by a conventional solid‐state sintering method in a reducing atmosphere (oxygen partial pressure of 1 × 10^?10 atm). All ceramics with a pure perovskite structure show the two‐phase coexistence zone composed of rhombohedral and tetragonal phase. Ta⁵⁺ ions substitute for Nb⁵⁺ ions on the B‐site, which results in a decrease in the R phase fraction in the two‐phase coexistence zone. The R‐T phase transition temperature moves to room temperature due to the substitution of Nb⁵⁺ ions by Ta⁵⁺ ions. A complex domain structure composed of small nano‐domains (~70 nm) formed inside large submicron domains (~200 nm) exists in KNNTa0.02‐0.045BNZ+0.4Mn ceramics, which can induce a strong dielectric‐diffused behavior and improve the piezoelectric properties. The temperature stability for the reverse piezoelectric constant for the KNNTaz‐0.045BNZ+0.4Mn ceramics can be improved at z = 0.02. Excellent piezoelectric properties (d₃₃ = 328 pC/N, and  = 475 pm/V at E_max = 20 kV/cm) were obtained for the KNNTa_0.02‐0.045BNZ+0.4Mn ceramics.     

First‐principles investigation of the thermodynamic stability of MB2 materials surfaces (M = Ti/Zr/Hf)

Some of the renewed interest in transition metal diborides (MB₂, M = Ti/Zr/Hf) arises from their potential use as matrices in ultrahigh‐temperature ceramic matrix composites (UHTCMCs). Crucial to the understanding of such composites is the study of the fiber/matrix interfaces, which in turn requires a deep knowledge of the surface structures and the thermodynamics of the matrix material. Here we investigate the surface stability of MB₂ compounds by first‐principles calculations. Five surfaces are stabilized when going from a M‐rich to a B‐rich environment, respectively (0001)_M, (100)_M, (101)_B(M), (113)_M and (0001)_B, with the highly stable (100)_M, (101)_B(M) and (113)_M surfaces being discussed here for the first time. The mechanism behind the surface stability is analyzed in terms of cleavage energy, surface strain and surface bonding states. Our results provide important information for a better understanding of the most likely surfaces exposed to the fibers in UHTCMCs, thereby for the construction of reliable interfaces and ultimately UHTCMCs models.     

Structure and Microwave Dielectric Behavior of A‐Site‐Doped Sr(1−1.5x)CexTiO3 Ceramics System

The ion valence state, phase composition, microstructure, and microwave dielectric properties of Sr_(1?1.5x)Ce_xTiO₃ (x = 0.1–0.67, SCT) ceramics were systematically investigated. Sr_(1?1.5x)Ce_xTiO₃ ceramics were produced with gradual structural evolution from a cubic to a tetragonal and turned to an orthorhombic structure in the range of 0.1 ≤ x ≤ 0.67. Above a critical Ce proportion (x = 0.4), microstructural changes and normal grain growth initially occurred. On the basis of chemical analysis results, the reduction of Ti⁴⁺ ions was hastened by tetravalent ions (Ce⁴⁺). By contrast, this reduction was inhibited by trivalent ions (Ce³⁺). The observed dielectric behavior was strongly influenced by phase composition, oxygen vacancies (), and defect dipoles, namely, () and (). Temperature stable ceramics sintered at 1350°C for 3 h in air yielded an intermediate value of dielectric constant (ε_r = 40), with the smallest reported value of temperature coefficient of resonant frequency (τ_f = +0.9 ppm/°C), and quality factor (Q × f = 5699 GHz) at x = 0.6.     

Ultralow dielectric loss in Y-doped SrTiO3 colossal permittivity ceramics via designing defect chemistry

Effects of doping of Y and sintering atmosphere on the dielectric properties of Sr_1-1.5xY_xTiO₃ ceramics (SYT, x = 0-0.014) were systematically investigated. The SYT14 (x = 0.014) ceramic sintered in N₂ attains a colossal permittivity (CP, Ɛ_r = 28 084@ 1kHz, 27 685@ 2MHz) and an ultralow dielectric loss (tanδ = 0.007@ 1kHz, 0.003@ 2MHz) at room temperature. Because of using of the A-site deficient, there are in SYT ceramics. Through the comprehensive analysis of dielectric responses, X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and complex impedance data, it is proved that doping of Y promotes the formation of (Y³⁺ are located at Sr²⁺ site), (Y³⁺ are located at Ti⁴⁺ site), and Ti³⁺, and sintering in reducing atmosphere of N₂ results in more (oxygen vacancy) and (strontium vacancy) generating in SYT ceramics. The defect dipoles, , , , , , and formed by introduced defects make charge carriers localized in SYT ceramics. The combined action of the massive defect dipoles is responsible for the ultralow tanδ and CP in SYT14 ceramics sintered in N₂.     

Demonstration of Copper Co‐Fired (Na,K)NbO3 Multilayer Structures for Piezoelectric Applications

A Li and Ta modified (Na, K)NbO₃ piezoelectric ceramic has been successfully co‐fired with inner copper electrodes in a reduced atmosphere. Highly dense NKN ceramics (95% relative density, 4.64 g/cm³) were obtained by sintering the samples in a low oxygen partial pressure (low pO₂) atmosphere at 1050°C. The poly(propylene carbonate) binder system was used to permit a clean burnout at low temperature in N₂ atmosphere, and also prevent the electrode copper particles from undergoing any oxidation. No interdiffusion of copper, chemical reactions, and/or carbon residues were observed in the grains, grain boundaries, or at the electrode–ceramic interface of the co‐fired samples from a detailed transmission electron microscopy (TEM) analysis. Dielectric and piezoelectric properties were characterized from those co‐fired prototyped samples. The samples displayed high relative dielectric permittivity above 800, with low dielectric loss about 3.6%. A normalized strain coefficient (max. strain/max. electric field) of = 220 pm/V was obtained under unipolar converse electromechanical measurement at 20 kV/cm. This paper presents the feasibility of co‐firing a Cu inner electrode with NKN ceramics toward multilayer lead‐free piezoelectric applications, providing an engineering route to narrow the performance differences between soft lead‐based piezoelectrics and lead‐free materials.     

A piezomicrobalance system for high‐temperature mass relaxation characterization of metal oxides: A case study of Pr‐doped ceria

A system for mass relaxation studies based on a gallium phosphate piezocrystal microbalance has been developed, built, and successfully used to characterize a representative mixed ionic and electronic conducting material. The apparatus is constructed to achieve reactor gas exchange times as short as 2 seconds and temporal resolution in mass measurement of 0.1 seconds. These characteristics enabled evaluation of mass relaxations that occurred on the 6 seconds time scale. Proof of concept for materials characterization capabilities of the system was carried out using 10% praseodymium‐doped cerium oxide (PCO), a material that undergoes, at selected temperatures and oxygen partial pressures, changes in mass but not in conductivity. Thin films were deposited on the piezocrystals via pulsed laser deposition (PLD). Mass relaxation curves were collected at 700°C upon application of a small step change in oxygen partial pressure, . Using two different films, the surface reaction constant, k_S, was obtained over the range from 10^?4 to 0.1 atm. Its value is found to vary between 9.7 × 10^?6 and 1.7 × 10^?4 cm/s, displaying a power law dependence on , with a law exponent of 0.67 ± 0.02, as averaged over the two sets of results. This steep dependence of k_S on is surprisingly independent of a change in dominant defect type within the range of measurement.     

Defect‐driven evolution of piezoelectric and ferroelectric properties in CuSb2O6‐doped K0.5Na0.5NbO3 lead‐free ceramics

Defect greatly affects the microscopic structure and electrical properties of perovskite piezoelectric ceramics, but the microscopic mechanism of defect‐driven macroscopic properties in the materials is not still completely comprehended. In this work, K_0.5Na_0.5NbO₃+x mol CuSb₂O₆ lead‐free piezoelectric ceramics were fabricated by a solid‐state reaction method and the defect‐driven evolution of piezoelectric and ferroelectric properties was studied. The addition of CuSb₂O₆ induces the formation of dimeric (DC1) and trimeric (DC2) defect dipoles. At low doping concentration of CuSb₂O₆ (0.5‐1.0 mol%), DC1 and DC2 coexist in the ceramics and harden the ceramics, inducing a constricted double P‐E loop and high Q_m of 895 at x=0.01. However, DC2 becomes more dominant in the ceramics with high concentration of CuSb₂O₆ (≥1.5 mol%) and thus leads to softening behavior of piezoelectricity and ferroelectricity as compared to the ceramic with x=0.01, giving a single slanted P‐E loop and relatively low Q_m of 206 at x=0.025. All ceramics exhibit relatively high d₃₃ of 106‐126 pC/N. Our study shows that the piezoelectricity and ferroelectricity of K_0.5Na_0.5NbO₃ ceramics can be tailored by controlling defect structure of the materials.     

Domain engineering enhanced microwave tunability in nonstoichiometric Ba0.8Sr0.2TiO3

Domain engineering via oxygen vacancy, , loading achieved by A/B modification as well as quenching treatment, was utilized for Ba_0.8Sr_0.2TiO₃ (0.8 BSTs) in an attempt to enhance the microwave tunable characteristics. For similar grain sizes, the domain sizes were notably reduced for all nonstoichiometric BSTs, indicating that the loaded (as a consequence of Ti defects, ) played a role in the nuclei for new domain walls. The tunability T at 100 MHz under a direct current field of 30 V/20 μm increased steadily as the domain size (d.s.) declined for all BSTs, regardless of the A/B ratio, due to the d.s. effect. The tunable characteristics in nonstoichiometric BSTs having a similar d.s. of ?190 nm were then compared. The tunability and tan δ decreased for A/B = 1.002 (0.2 mol% Ti defects). The introduced formed pinning centers that restricted domain wall motion, leading directly to lower tunability and smaller dielectric loss. However, ‐overloaded samples (i.e., A/B ≥ 1.005) exhibited increased values for tan δ due to conduction in the domains. The quench treatment of 0.8 BST (with A/B = 1.002) samples resulted in a d.s. reduction from 191 to 170 nm. These quenched specimens showed greater tunability, T_total, originating from the strengthened dipole contribution, T_dipole, as a consequence of the d.s. effect. The tan δ of the quenched specimens was essentially unchanged, indicating a homogenous distribution via the quench, effectively reducing the mobile (which contributes to electrical conduction) in the domains. Consequently, the achieved figure of merit via domain engineering was 2.25 at 100 MHz for the quenched BST with A/B = 1.002, which was 1.54 times larger than that of unmodified BST.     

Layered Structure Induced Anisotropic Low‐Energy Recoils in Ti3SiC2

Low‐energy recoil events in Ti₃SiC₂ are studied using ab initio molecular dynamics simulations. We find that the threshold displacement energies are orientation dependent because of anisotropic structural and/or bonding characteristic. For Ti and Si in the Ti–Si layer with weak bonds that have mixed covalent, ionic, and metallic characteristic, the threshold displacement energies for recoils perpendicular to the basal planes are larger than those parallel to the basal planes, which is an obvious layered‐structure‐related behavior. The calculated minimum threshold displacement energies are 7 eV for the C recoil along the direction, 26 eV for the Si recoil along the direction, 24 eV for the Ti in the Ti–C layer along the direction and 23 eV for the Ti in the Ti–Si layer along the direction. These results will advance the understanding of the cascade processes of Ti₃SiC₂ under irradiation and are expected to yield new perspective on the MAX phase family that includes more than 100 compounds.     

Growth of diopside crystals in CMAS glass‐ceramics using Cr2O3 as a nucleating agent

CaO–Al₂O₃–MgO–SiO₂ (CAMS)‐based glass‐ceramics were prepared using body crystallization method. Adding Cr₂O₃ into the ceramics not only effectively lowered the crystallization temperature, but also led to significant grain refinement of diopside that crystallized in the CAMS glass‐ceramic after crystallization treatment at 900°C for 2 hours. Experimental work verified that the epitaxial growth of the diopside on the spinel particles, which formed during nucleation treatment when fabricating the glass‐ceramics, facilitated the heterogeneous nucleation of diopside on the spinel and refined the diopside. In addition, two energetically favored crystallographic orientation relationships between the epitaxial growth diopside and spinel were experimentally observed. They are //[001]_diopside,////(200)_diopside and //[101]_diopside, (311)_spinel//. These two novel results can be potentially used to develop new glass‐ceramic materials with improved performance.