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Journal of Inorganic Materials
Contents
2022
Volume: 37 Issue 6
13 Article(s)
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RESEARCH ARTICLE
Columnar Nanograined BaTiO
3
Ferroelectric Thin Films Integrated on Si with a Sizable Dielectric Tunability
Yuyao ZHAO, and Jun OUYANG
BaTiO3 has a wide range of applications in microelectromechanical systems and integrated circuits due to its excellent dielectric, ferroelectric, piezoelectric, and pyroelectric properties. For the applied research and device applications of BaTiO3 films, reducing its deposition temperature to be compatible with the CM
BaTiO
3
has a wide range of applications in microelectromechanical systems and integrated circuits due to its excellent dielectric, ferroelectric, piezoelectric, and pyroelectric properties. For the applied research and device applications of BaTiO
3
films, reducing its deposition temperature to be compatible with the CMOS-Si technology is an important Challenge. Here, with the help of a LaNiO
3
buffer layer which has a closely-matched lattice with BaTiO
3
, (001)-textured BaTiO
3
films were sputter-deposited at 450 ℃ on single crystalline Si(100) substrates, which consisting of well-cryotallized, evenly-distributed columnar nanograins with an average grain size of 27 nm. Our result showed that this deposition temperature can maintain the columnar nanograin structure with a relatively large grain size, leading to a good ferroelectric performance. In addition, a small residual strain on Si was also helpful to improve its ferroelectric and dielectric properties. The remnant polarization and saturated polarization of these BaTiO
3
films reached 7 and 43 μC·cm
-2
, respectively, while leakage current densities were as low as 10
-5
A·cm
-2
at an applied electric field of 0.8 MV·cm
-1
. These BaTiO
3
films also displayed excellent frequency stability with a low dielectric loss in which relative dielectric constant measured to be ~155 at 1 kHz, slightly being reduced to ~145 after increasing the frequency to 1 MHz. Meanwhile, the dielectric loss slightly increased from 0.01 at 1 kHz to 0.03 at 1 MHz. Lastly, through capacitance-voltage (
C
-
V
) tests, these films exhibited a large dielectric tunability of~51% and a figure of merit (FOM) of ~17 (@1 MHz). These films have a good potential for applications in tunable dielectrics..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 596 (2022)
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Field-induced Strain Property of Lead-free Ferroelectric Ceramics Based on Sodium Bismuth Titanate
Huiping YANG, Xuefan ZHOU, Haojie FANG, Xiaoyun ZHANG, Hang LUO, and Dou ZHANG
Piezoelectric actuators have advantages of fast response, high positioning accuracy, small size, and have received widespread attention in the field of precision drives. Lead-based piezoelectric actuators occupy the main commercial market. To avoid the use of the harmful element lead, a lead-free piezoelectric material
Piezoelectric actuators have advantages of fast response, high positioning accuracy, small size, and have received widespread attention in the field of precision drives. Lead-based piezoelectric actuators occupy the main commercial market. To avoid the use of the harmful element lead, a lead-free piezoelectric materials and actuators must be developed. Among them, bismuth sodium titanate (Bi
0.5
Na
0.5
)TiO
3
(BNT), was reported but it has some disadvantages of higher driving voltage, larger hysteresis, and poor temperature stability. To optimize the strain performance of the lead-free actuator, this study adopted the solid-phase reaction method to prepare (1-
x
) {0.76(Bi
0.5
Na
0.5
)TiO
3
- 0.24SrTiO
3
}-
x
NaNbO
3
(BNT-ST-
x
NN,
x
=0-0.03) lead-free ferroelectric ceramics, systematically studied its field- induced strain performance. The results show that when
x
=0.01, the strain value of the ceramic can reach 0.278% under a low electric field (
E
= 4 kV/mm), and the piezoelectric coefficient
d
*
33
is as high as 695 pm/V. Meanwhile, the ceramic is at the non-ergodic/ergodic relaxation phase boundary, and the electric field induced relaxor-ferroelectric phase transition leads to large field-induced strain. Compared with
x
=0.01, the strain value at
x
=0.02 is 0.249%, which is slightly reduced, but the hysteresis is significantly reduced to 43% of the comparator. In addition, the strain remains stable in the temperature range of 25-100 ℃. This study shows that introduction of SrTiO
3
and NaNbO
3
into BNT can increase the field-induced strain value while maintaining a low driving voltage and good temperature stability, indicating suitable for the development of piezoelectric actuators..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 603 (2022)
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Electrochromic Property of Perovskite Ceramic Films
Zhihang HUANG, Guanhongwei TENG, Peng TIE, and Desong FAN
Perovskite manganese oxide (PMO) has attracted extensive attention in the field of heat dissipation because of its discoloration stimulated by external conditions. At present, most of the researchs on the discoloration characteristics of PMO is based on temperature excitation, and there still lacks of heat dissipation
Perovskite manganese oxide (PMO) has attracted extensive attention in the field of heat dissipation because of its discoloration stimulated by external conditions. At present, most of the researchs on the discoloration characteristics of PMO is based on temperature excitation, and there still lacks of heat dissipation equipment excited by electric field. In addition, because the electric field excitation is accompanied by Joule heat, electrochromic property of PMO materials has not been clearly proved. In view of the above challenges, here an electrical modification method for PMO materials is proposed by using influence of electric field excitation on Mn elements in PMO. Thermochromic property of PMO was greatly weakened by electrical modification, and then La
0.7
Ca
0.25
K
0.05
MnO
3
(LCKMO) can eliminate the influence of Joule heat in electric field excitation experiment. We studied the thermochromic and electrochromic properties of LCKMO before and after electrical modification. Emittance of LCKMO before electrical modification increases with the increase of temperature with the maximum increment at 17%. After being excited by 21 V electric field, the emittance increases by 15%, 16%, 10%, 0.6% and 1.4% at 173, 203, 243, 273, and 373 K, respectively. The thermochromic property of electrically modified LCKMO is greatly weakened, and its emittance increases by 10.7% and 9.3% at 273 and 373 K, respectively, after being excited by 21 V electric field. The experimental results before and after electrical modification show that LCKMO has electrochromic property, and there is an obvious regulation mechanism of electric field excitation on the emissivity. Therefore the electrical modification method for PMO materials can not only enable the electrochromic study of PMO materials without the influence of Joule heat, but also provides a new possibility for regulation of the thermochromic property of PMO materials..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 611 (2022)
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Preparation and Properties of Barium Titanate/Calcium Silicate Composite Bioactive Piezoelectric Ceramics
Ziqin WEI, Xiang XIA, Qin LI, Guorong LI, and Jiang CHANG
Electrical signals generated by piezoelectric materials can promote proliferation and differentiation of osteoblasts, but they can’t induce mineralization, while bioactive materials can induce the deposition of bone like hydroxyapatite in physiological environment, but can not generate electrical signal to promote oste
Electrical signals generated by piezoelectric materials can promote proliferation and differentiation of osteoblasts, but they can’t induce mineralization, while bioactive materials can induce the deposition of bone like hydroxyapatite in physiological environment, but can not generate electrical signal to promote osteogenesis. Therefore, it is of great significance to develop a composite bioactive piezoelectric material that can not only generate electrical signals, but also induce mineralization and deposition. Here, we used barium titanate as piezoelectric component and calcium silicate as bioactive component to prepare barium titanate/calcium silicate composite as bioactive/piezoelectric ceramics by solid-state sintering method. Piezoelectric properties of the ceramics were tested, and the ability of inducing mineralization was evaluated by
in vitro
mineralization experiment. The experimental results show that when the content of calcium silicate reaches 30%, the composite ceramics still have certain piezoelectric property (
d
33
=4 pC·N
-1
), and can induce the deposition of calcium phosphate in simulated body fluid. Therefore, the combination of barium titanate and calcium silicate can synchronously afford piezoelectric and biological activities, which provides a new choice for bone repair materials..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 617 (2022)
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Binderless Layered BN Toughened cBN for Ultra-precision Cutting
Junyun CHEN, Lei SUN, Tianye JIN, Kun LUO, Zhisheng ZHAO, and Yongjun TIAN
Poor toughness and high synthesis pressure of binderless cBN limits its application in the field of cutting tool. To enhance its toughness, an advanced layered BN toughened cBN (Lt-cBN) bulk was developed under industrial pressure. Then, the cutting performance and wear resistance of Lt-cBN was analyzed based on the un
Poor toughness and high synthesis pressure of binderless cBN limits its application in the field of cutting tool. To enhance its toughness, an advanced layered BN toughened cBN (Lt-cBN) bulk was developed under industrial pressure. Then, the cutting performance and wear resistance of Lt-cBN was analyzed based on the unique microstructure during tungsten carbide cutting. It is found that the Lt-cBN reaches a high fracture toughness of 8.5 MPa·m
1/2
, and is capable of realizing ultra-precision cutting of tungsten carbide with smooth surface of roughness lower than
R
a
10 nm. The layered BN at the intersection of cBN grains within Lt-cBN contributes to the enhanced toughness, which further slows down the transformation of amorphization as well as the wear rate of the surface layer. Thus Lt-cBN exhibits better cutting performance and wear resistance in contrast to commercial binderless pure cBN material. The wear of Lt-cBN can be explained by the soft partially amorphous layer formed on the flank surface being rubbed and continuously removed in the form of abrasive wear..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 623 (2022)
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High Temperature Tensile Property of Domestic 550-grade Continuous Alumina Ceramic Fiber
Xingang WANG, Qingqing YANG, Genlian LIN, Wei GAO, Fulin QIN, Rongzhen LI, Zhuang KANG, Xiaofei WANG, Danyu JIANG, and Jina YAN
Oxide fiber has good thermostability and oxidation resistance at high temperature, is one of the important candidates for the reinforcements of composites for aerospace field. The tensile property at high temperature is one of the critical properties of oxide fiber used in harsh environment, but the related research ab
Oxide fiber has good thermostability and oxidation resistance at high temperature, is one of the important candidates for the reinforcements of composites for aerospace field. The tensile property at high temperature is one of the critical properties of oxide fiber used in harsh environment, but the related research about domestic 550-grade fiber is rarely reported. Here the tensile property of domestic 550-grade continuous alumina fiber at high temperature and its room temperature tensile property after heat treatment were studied. Relationships between the tensile strength and the phase transition, the microstructures, as well as their internal mechanism were investegated. The results showed that the fiber multifilament and filaments had relatively high tensile strength with strength retention rate up to 1100 ℃. The poor thermostability of amorphous SiO
2
had obviously adverse effect on the tensile property of the fiber at temperature above 1200 ℃. Importantly, at the critical phase transition temperature (1300 ℃) mullite plase was formed, which could improve the fiber tensile strength at 1250-1400 ℃. This work demonstrated that the tensile strength of SIC550 fiber at 1100 ℃ was close to that of Nextel 720 and CeraFib by considering the effect of different gauge length..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 629 (2022)
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Effect of Boron Carbide Particle Size Distribution on the Microstructure and Properties of Reaction Bonded Boron Carbide Ceramic Composites by Silicon Infiltration
Qian XIA, Shihao SUN, Yiliang ZHAO, Cuiping ZHANG, Hongqiang RU, Wei WANG, and Xinyan YUE
Effect of particle size of boron carbide raw material on the phase composition, microstructure and properties of reaction bonded boron carbide composites was investigated. It was found that particle gradation can make the powder packing more compact and effectively improve the volume density of green body, decreasing t
Effect of particle size of boron carbide raw material on the phase composition, microstructure and properties of reaction bonded boron carbide composites was investigated. It was found that particle gradation can make the powder packing more compact and effectively improve the volume density of green body, decreasing the content of free Si in the composites. Addition of coarse particles can reduce the reaction between B
4
C and Si, which can generate SiC phase. When the weight ratio of B
4
C powders with different particle sizes (3.5, 14, 28, 45 μm) is 1.5 : 4 : 1.5 : 3, the Vickers hardness, flexure strength, fracture toughness and volume density of the composites are (29±5) GPa, (320±32) MPa, (3.9±0.2) MPa·m
1/2
and 2.51g/cm
3
, respectively. The retard of reaction between B
4
C and Si, and the decrease of free Si content along with the shrinkage of size of Si zone in the composites, are the main reasons for the improvement of the composite mechanical properties..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 636 (2022)
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Tribological Properties of Plasma Sprayed TiC-Graphite Composite Coatings
Du HONG, Yaran NIU, Hong LI, Xin ZHONG, and Xuebin ZHENG
Plasma sprayed TiC coating has now been a frequent choice for wear-resistant applications in extreme environments owing to its good comprehensive performance. Meanwhile, graphite is an excellent self-lubricating material. Here, spherical TiC-Graphite composite powders with different contents of graphite (1.25%, 2.5%, 5
Plasma sprayed TiC coating has now been a frequent choice for wear-resistant applications in extreme environments owing to its good comprehensive performance. Meanwhile, graphite is an excellent self-lubricating material. Here, spherical TiC-Graphite composite powders with different contents of graphite (1.25%, 2.5%, 5%, and 10% in mass) were fabricated by spray drying and vacuum sintering, and then TiC-Graphite composite coatings were prepared by atmospheric plasma spray (APS) technology. The phase composition, microstructure and mechanical properties of the coatings were characterized, and its tribological performances were evaluated. The results showed that the TiC-Graphite coatings were mainly composed of TiC and graphite phases. With the increase of graphite addition, the micro-cracks in the section and the roughness of the TiC-Graphite coatings increased while the hardness gradually decreased. Compared with low load, graphite had more significant effect on wear performance of the TiC coating under high load. Under the load of 50 N, wear rate of the TiC-Graphite coating first decreased and then increased, but the friction coefficient kept decreasing with the increase of graphite addition. When the graphite addition was 0.25%, the minimum wear rate of 0.67×10
-5
mm
3
/(N·m) was obtained, whereas the friction coefficient was 0.35, which were reduced by 72.4% and 27.8% compared with the pure TiC coating, respectively..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 643 (2022)
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First-principles Study on Interface of Reduced Graphene Oxide Reinforced Aluminum Matrix Composites
Ming SUN, Puzhen SHAO, Kai SUN, Jianhua HUANG, Qiang ZHANG, Ziyang XIU, Haiying XIAO, and Gaohui WU
An “aluminum/graphene oxide/aluminum (Al/GO/Al)” interface model with different carbon/oxygen ratio or with different defects was established. Effects of oxygen-containing functional groups and different defects on the interface of reduced graphene oxide/aluminum composites was studied using first principle method base
An “aluminum/graphene oxide/aluminum (Al/GO/Al)” interface model with different carbon/oxygen ratio or with different defects was established. Effects of oxygen-containing functional groups and different defects on the interface of reduced graphene oxide/aluminum composites was studied using first principle method based on density functional theory (DFT). The results show that the epoxy group is better than carbon atom to produce obvious charge interaction with aluminum atom in the interface model of Al/GO/Al. The net charge of oxygen atom is -0.98 e while aluminum atom is 0.46 e, which is conducive to the interfacial bonding between reduced graphene oxide (RGO) and aluminum matrix in composites. When the defects exists, the net charge of carbon atoms at the defects in the Al/GO/Al interface model is in the range of -0.05 e to -0.38 e. Interaction between epoxy group and carbon atoms is weak, while interaction between epoxy group and aluminum atoms is significantly intensified. The existence of epoxy group can inhibit reaction between carbon atom and aluminum atom in the vacancy defects, and protect integrity of carbon structure in RGO with vacancy defects. Therefore, this research may provide theoretical guidance for development of high-performance Al/GO/Al matrix composites..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 651 (2022)
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Halogenated Ti
3
C
2
MXene as High Capacity Electrode Material for Li-ion Batteries
Meixia XIAO, Miaomiao LI, Erhong SONG, Haiyang SONG, Zhao LI, and Jiaying BI
MXenes have been widely studied for their excellent specific surface area, high conductivity and composition tunability, which have been used as a highly efficient electrode material for lithium-ion batteries (LIBs). However, limited storage capacity and severe lattice expansion caused by Li-ions diffusion restrict the
MXenes have been widely studied for their excellent specific surface area, high conductivity and composition tunability, which have been used as a highly efficient electrode material for lithium-ion batteries (LIBs). However, limited storage capacity and severe lattice expansion caused by Li-ions diffusion restrict the application of MXenes as electrode materials. Here, Ti
3
C
2
MXenes with surface halogenation (fluorination, chlorination and bromination) as representative MXene materials were designed. Effects of surface functionalization on the atomic structures, electronic properties, mechanical properties, and electrochemical performance of Ti
3
C
2
T
2
(T = F, Cl and Br) anode in LIBs were investigated using first-principles calculations based on density functional theory with van der Waals correction. The results reveal that Ti
3
C
2
T
2
MXenes exhibit metallic conductivity with improved structural stability and mechanical strength. Compared with Ti
3
C
2
F
2
and Ti
3
C
2
Br
2
, Ti
3
C
2
Cl
2
exhibits the large elastic modulus (321.70 and 329.43 N/m along
x
and
y
directions, respectively), low diffusion barrier (0.275 eV), high open circuit voltage (0.54 eV), and storage capacity (674.21 mA·h/g) with stoichiometric ratio of Ti
3
C
2
Cl
2
Li
6
, which renders the enhanced rate performance and endures the repeated lattice expansion and contraction during the charge/ discharge process. Moreover, surface chlorination yields expanded interlayer spacing, which can improve Li-ion accessibility and fast charge-discharge rate in Ti
3
C
2
Cl
2
. The research demonstrates that Cl
-
terminated Ti
3
C
2
is a promising anode material, and provides effective and reversible routes to engineering other MXenes as anode materials for LIBs..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 660 (2022)
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Microstructure and Thermal Quenching Characteristics of Na
1-
x
M
x
CaEu(WO
4
)
3
(M=Li, K) Red Phosphor
Xufeng GUAN, Guifang LI, and Yunge WEI
Red phosphors play a vital role in improving the photoluminescence properties of white LEDs (w-LEDs). In order to prepare high efficiency and stability red phosphor for commercial LED chips, a series of tetragonal scheelite structure Na1-xMxCaEu(WO4)3 (M=Li, K) red phosphors were synthesized by a solid state reaction m
Red phosphors play a vital role in improving the photoluminescence properties of white LEDs (w-LEDs). In order to prepare high efficiency and stability red phosphor for commercial LED chips, a series of tetragonal scheelite structure Na
1-
x
M
x
CaEu(WO
4
)
3
(M=Li, K) red phosphors were synthesized by a solid state reaction method. The effect of Li
+
and K
+
doping on the crystal structure, photoluminescence properties and thermal quenching characteristics of NaCaEu(WO
4
)
3
phosphor were investigated systematically. Rietveld refinement results show that the doping of Li
+
and K
+
exerts change on the tetragonal scheelite structure of the NaCaEu(WO
4
)
3
host, but forms the solid solution, and results in the regular change in the lattice constant. The photoluminescence spectra show that under the excitation of near ultraviolet light at 395 nm, the phosphors exhibit a typical red emission, with the strongest emission peak at 617 nm, corresponding to the
5
D
0
→
7
F
2
transition of Eu
3+
ion, which indicates that Eu
3+
is situated in non-central symmetric lattices in NaCaEu(WO
4
)
3
host. It is noteworthy that the doping of Li
+
and K
+
effectively improves the emission intensity of the NaCaEu(WO
4
)
3
phosphor. When the doping concentration (molar percent) of Li
+
and K
+
is 100% and 30%, respectively, both the emission intensity and the color purity realize optimum. In addition, thermal stability and thermal quenching characteristics of Na
1-
x
M
x
CaEu(WO
4
)
3
(M=Li, K) phosphors were studied. The results show that both Li
+
and K
+
doped phosphors display excellent thermal quenching, and when the Li
+
doping concentration (molar percent) is 100%, LiCaEu(WO
4
)
3
phosphor processes the best thermal quenching. All results demonstrate that Na
1-
x
M
x
CaEu(WO
4
)
3
(M= Li, K) red phosphors can be applied to high-power NUV (Near ultraviolet) excited white light emitting diodes potentially..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 676 (2022)
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RESEARCH LETTER
Stability of Low-index Surfaces of Cs
2
SnI
6
Studied by First-principles Calculations
Aming LIN, and Yiyang SUN
Cs2SnI6 is a stable and environmentally friendly halide perovskite material with great potential for photovoltaic and optoelectronic applications. While the surface properties are of paramount importance for device fabrications, there have been no such theoretical studies on this material. Using density functional theo
Cs
2
SnI
6
is a stable and environmentally friendly halide perovskite material with great potential for photovoltaic and optoelectronic applications. While the surface properties are of paramount importance for device fabrications, there have been no such theoretical studies on this material. Using density functional theory calculations with the SCAN+rVV10 functional, the (001), (011) and (111) surfaces of Cs
2
SnI
6
were studied to reveal their thermodynamic stability. We constructed seven models for these surfaces, including two along the (001) orientation (CsI
2
- and SnI
4
-terminated surfaces), two along the (011) orientation (I
4
- and Cs
2
SnI
2
-terminated surfaces) and three along the (111) orientation (non-stoichiometric CsI
3
-, Sn- and stoichiometric CsI
3
-terminated surfaces). Because most of the surfaces are non-stoichiometric, their relative stability depends on the experimental preparation condition, which is reflected by the chemical potentials of the constituent elements in the calculation. By determining the allowed chemical potential region, the thermodynamic stability of these Cs
2
SnI
6
surfaces is analyzed. The results show that the surface energies of the (001) and (011) surfaces are affected by the chemical potentials, while the stoichiometric CsI
3
-terminated (111) surface is unaffected by the chemical potentials and is energetically the most stable surface of Cs
2
SnI
6
. Thus, the observed exposure of (111) surface of Cs
2
SnI
6
crystals in several recent experiments is determined to be driven by thermodynamics..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 691 (2022)
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REVIEW
Recent Progress on Additive Manufacturing of Piezoelectric Ceramics
Bo NAN, Jiadong ZANG, Wenlong LU, Tingwang YANG, Shengwei ZHANG, and Haibo ZHANG
Piezoelectric ceramic is a type of functional ceramic, which is able to convert the mechanical signal and the electronic signal mutually. Composed of piezoelectric ceramics and organic phase, piezoelectric composites have different kinds of connectivities, which not only determine the diverse applications of piezoelect
Piezoelectric ceramic is a type of functional ceramic, which is able to convert the mechanical signal and the electronic signal mutually. Composed of piezoelectric ceramics and organic phase, piezoelectric composites have different kinds of connectivities, which not only determine the diverse applications of piezoelectric devices, but also promote the development of various shaping techniques in manufacturing piezoelectric materials and devices. In comparison with the traditional shaping methods, the most distinguishable advantage of additive manufacturing lies in its ability of quickly shaping a small batch of samples into geometrically complex designs without a mould, which makes it a highly suitable technique for investigating piezoelectric ceramics and its derivative devices in different kinds of connectivities. Meanwhile, the final additively manufactured samples require only tiny post-processing, have a high rate of utilization of the raw material and do not need cutting fluid during manufacturing. Due to the above-mentioned advantages, it attracts the widespread concerns from both academic and industrial communities. When focusing in the field of additive manufacturing ceramics, the data of scientific reports in additive manufacturing functional ceramics and devices prove that it is still in a growing period. In the perspective of different additive manufacturing techniques, this article discusses and compares additive manufacturing of both lead-free and lead-based piezoelectric ceramics in the aspects of their historical development of each technique, preparation of the raw materials, geometrical designs, measurement of functional properties, and applications of the printed samples, and forecasts the future development based on the current benefits and drawbacks of each additive manufacturing technique..
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Journal of Inorganic Materials
Publication Date: Jun. 20, 2022
Vol. 37, Issue 6, 585 (2022)
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