b o l e t í n d e l a s o c i e d a d e s p a ñ o l a d e c e r á m i c a y v i d r i o 6 2 (2 0 2 3) 468–478

www.elsevier.es/bsecv

Structural and electrical properties of Zr-doped

K0.48 Na0.52 NbO3 ceramics: “Hard” lead-free
piezoelectric

Héctor Beltrán-Mir a,∗ , Xavier Vendrell b,c , Emerson Luiz dos Santos Veiga a ,
Lourdes Mestres c , Eloísa Cordoncillo a
a Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, Castellón, Spain
b Universitat Politècnica de Catalunya, Nanoenginyeria de materials aplicats a l’energia, Sant Adrià de Besòs, Spain
c Departamento de Química Inorgánica y Orgánica, Sección Inorgánica, Facultad de Química, Universitat de Barcelona, Barcelona, Spain

a r t i c l e i n f o a b s t r a c t

Article history: The structural and electrical properties of K0.48 Na0.52 Nb1−x Zrx O3−ı (x = 0–0.04) ceramics
Received 22 September 2022 prepared by the conventional solid-state reaction method were studied. Pellets with compo-
Accepted 9 December 2022 sition x ≤ 0.03 sintered at 1125 ◦ C for 2 h showed single-phase of potassium sodium niobate
Available online 19 January 2023 (KNN) perovskite structure. Based on X-ray diffraction and Raman results, a mixture of
orthorhombic and monoclinic phases was observed in intermediate compositions. The
Keywords: addition of Zr improved the sinterability and the “hard” piezoelectric properties of KNN,
Hard lead-free ceramics increasing the Ec and Qm values. The composition with x = 0.03 presented the highest permit-
Piezoelectric materials tivity at room temperature, εr  = 363 and the lowest dielectric losses, tan ı = 0.027. Moreover,
Impedance spectroscopy it was the sample with the highest Qm and d33 values, with Qm = 1781 and d33 = 82 pC/N. It
Dopants/doping was therefore the best compositions to obtain a “hard” piezoelectric material based on Zr-
Potassium sodium niobite KNN doped KNN, which makes it promising candidate for use as “hard” lead-free piezoelectric
material for high power applications.
© 2023 The Authors. Published by Elsevier España, S.L.U. on behalf of SECV. This is an
open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

Propiedades estructurales y eléctricas de cerámicas K0,48 Na0,52 NbO3

dopadas con Zr: piezoeléctrico «duro» libre de plomo

r e s u m e n

Palabras clave: Se estudiaron las propiedades estructurales y eléctricas de cerámicas basadas en

Cerámicas «duras» libres de plomo
Materiales piezoeléctricos
Espectroscopia de impedancias
Dopantes
Niobato de potasio y sodio KNN
K0,48 Na0,52 Nb1−x Zrx O3−ı (x = 0-0,04) preparadas por el método convencional de reacción en
estado sólido. Las pastillas sinterizadas a 1.125 ◦ C durante 2 h con composición x ≤ 0,03
mostraron una estructura monofásica de perovsquita del óxido mixto de niobio, potasio y
sodio (KNN). Según los resultados de difracción de rayos X y Raman, se observó una mezcla
de fases ortorrómbica y monoclínica en las composiciones intermedias. La adición de Zr

∗
Corresponding author.
E-mail address: mir@uji.es (H. Beltrán-Mir).
https://doi.org/10.1016/j.bsecv.2022.12.001
0366-3175/© 2023 The Authors. Published by Elsevier España, S.L.U. on behalf of SECV. This is an open access article under the CC BY
license (http://creativecommons.org/licenses/by/4.0/).
UNIVERSIDAD AUTONOMA DE BAJA CALIFORNIA
FACULTAD DE INGENIERIA Y TECNOLOGIA
VALLE DE LAS PALMAS

MATERIA: Materiales eléctricos

M1.1 “Resumen de Clasificación y Enlaces”.
Profesor: Benjamín González
Grupo:539
Alumna: Parrasales Torres Perla Yeraldinne

Tijuana B.C a 27 de agosto del 2023

Clasificación:
La clasificación se basa en la tabla periódica, que organiza los elementos en filas y
columnas según su número atómico y propiedades. Las filas se llaman periodos y las
columnas grupos. Los elementos en un mismo grupo tienden a tener propiedades similares,
ya que comparten configuraciones electrónicas externas. Los elementos se pueden clasificar
en metales, no metales y metaloides. Los metales tienden a ser buenos conductores de calor
y electricidad, mientras que los no metales tienden a ser malos conductores y a menudo
forman compuestos iónicos o covalentes. Los metaloides exhiben propiedades intermedias.

Enlace:
Los átomos se enlazan para alcanzar una configuración electrónica más estable. Los enlaces
iónicos se forman mediante la transferencia de electrones de un átomo a otro, creando iones
con carga eléctrica que se atraen entre sí. Los enlaces covalentes implican el intercambio de
electrones para completar las capas de valencia de ambos átomos. Los enlaces pueden ser
polares (cuando los electrones se comparten de manera desigual) o no polares (cuando se
comparten equitativamente).

Tipos de enlace:

Enlace covalente: Los átomos comparten electrones para llenar sus capas de valencia.
Puede ser simple, doble o triple según el número de pares de electrones compartidos.
Enlace iónico: Se forma entre elementos con gran diferencia de electronegatividad. Un
átomo dona electrones (cationes) y otro los acepta (aniones), atrayéndose
electrostáticamente.
Enlace metálico: Ocurre en metales, donde los electrones se comparten entre muchos
átomos, creando una "nube" de electrones móviles que contribuye a las propiedades
metálicas como la conductividad eléctrica.
Importancia:
La comprensión de la clasificación y el enlace es crucial para predecir propiedades de
elementos y compuestos, así como para diseñar nuevos materiales y entender reacciones
químicas. Los enlaces determinan las formas y propiedades de las moléculas y son
esenciales para la formación de materiales en diversas áreas, desde productos farmacéuticos
hasta materiales electrónicos y estructuras biológicas.
 UNIVERSIDAD AUTONOMA DE BAJA CALIFORNIA
FACULTAD DE INGENIERIA Y TECNOLOGIA
VALLE DE LAS PALMAS

METERIALES ELECTRICOS
PROFESOR BEJAMIN GONZALEZ VIZCARRA

RESUMEN
ESTRUCUTRA CRISTALINA Y DEFECTOS

GRUPO :539
PARRASALES TORRES PERLA YERALDINNE 01296999

TIJUANA B.C, A 03 DE SEPTIEMBRE DEL 2023

Energía de enlace y distancia interatómica
Distancia interatómica. - Es el espacia miento interatómico ó separación interatómica en
material solido e aproximadamente igual al diámetro atómico Energía de enlace. - Es la
energía que se requiere para formar o romper un enlace. De tal modo que los materiales con
una alta energía de enlaces están asociados con puntos de fusión altos. Con esta energía están
asociadas las siguientes propiedades
Orden de corto alcance Vs Orden de largo alcance
Definición de corto alcance (SRO, short range order).- Es el arreglo de átomos que solo se
extiende a su vecindad inmediata. Gases, vidrios, polímeros
Definición de largo alcance (LRO, Long range order).- Es el arreglo de átomos que se
extiende a dimensiones mayores más de 100 nm. En estos materiales los átomos iones forman
un patrón regular y repetitivo semejante a una red tridimensional formando un material
cristalino
Monocristalino (chips de computadoras ó componentes electrónicos)
Policristalino.- Esta formado por muchos cristales pequeños con diversas orientaciones en el
espacio(presentan límites de grano).
El orden de los materiales policristalinos solo se puede detectar con difracción de rayos X
(DRX) o de electrones. Cristales Líquidos. - Son materiales poliméricos (amorfos), sin
embargo cuando se les aplica un estímulo externo algunas moléculas se alinean y forman
pequeñas regiones cristalinas. Vidrios metálicos. - Velocidades de enfriamiento rápido
Redes de BRAVAIS
Red. - Conexión de puntos llamados puntos de red, las cuales pueden ser uni, bi ó
tridimensional.
Estructura cristalina. - Es un grupo de uno ó más átomos ubicados en forma determinada
entre si y asociados con cada punto de red
Celda Unitaria. - Es la subdivisión de una red que sigue conservando las características
generales de toda la red.
Sistema Cristalino. - Arreglos de largo alcance que llenan el espacio
tridimensional Cubico, tetragonal, ortorrómbico, romboédrico, hexagonal, monoclínico y
triclínico.
Numero de Átomos por celda unitaria
BCC1 átomo en el centro+1/8 (8 átomos de los vértices = 2 átomos por celda
FCC½ (6 átomos de lascaras) +1/8 (8 átomos de los vértices = 4 átomos por celda
HCP½ (2 átomos de las bases) +1/6 (12 átomos de los vértices + 3 átomos en el interior de
la celda = 6átomos por celda
Defectos en las Estructuras Cristalinas:
Los defectos son irregularidades o imperfecciones en una estructura cristalina que pueden ser
inherentes o surgir durante la formación o manipulación de un material. Estos defectos
pueden tener un impacto significativo en las propiedades de los materiales. Los tipos de
defectos incluyen:
Defectos puntuales: Ocurren en lugares específicos de la red cristalina.
Defectos de vacancia: Átomos faltantes en la estructura.
Defectos intersticiales: Átomos adicionales que ocupan lugares entre los átomos regulares.
Defectos de sustitución: Átomos de una especie reemplazan a los de otra en la estructura.
Defectos lineales: Son defectos unidimensionales que ocurren en ciertas direcciones de la
red.
Dislocaciones: Son defectos que involucran desplazamientos en la disposición de átomos a
lo largo de una línea.
Defectos de superficie: Se producen en las interfaces entre diferentes regiones cristalinas o
entre un cristal y su entorno.
Límites de grano: Límites que separan regiones de cristal con orientaciones cristalinas
ligeramente diferentes.
Superficies libres: La superficie externa de un cristal.
Defectos de contorno de grano: Irregularidades en los límites de grano.
Defectos tridimensionales: Afectan a toda la estructura cristalina en lugar de estar confinados
a una dimensión específica.
Porosidad: Presencia de espacios vacíos en la estructura cristalina.
Estos defectos pueden afectar las propiedades mecánicas, eléctricas, magnéticas y ópticas de
los materiales, y su estudio es esencial para comprender y controlar el comportamiento de
los materiales en aplicaciones prácticas.
 UNIVERSIDAD AUTONOMA DE BAJA CALIFORNIA
FACULTAD DE INGENIERIA Y TECNOLOGIA
VALLE DE LAS PALMAS

METERIALES ELECTRICOS
PROFESOR BEJAMIN GONZALEZ VIZCARRA
RESUMEN

MATERIALES DIELECTRICOS

ESTRUCUTRA CRISTALINA Y DEFECTOS

GRUPO :539
PARRASALES TORRES PERLA YERALDINNE 01296999
TIJUANA B.C, A 01 DE octubre de DEL 2023.
Los materiales dieléctricos son un tema fundamental en la física y la ingeniería que se relaciona con
el comportamiento de materiales no conductores en campos eléctricos. Aquí tienes un resumen de los
temas relacionados con materiales dieléctricos:

Definición y Características: Los materiales dieléctricos son sustancias que no conducen corriente
eléctrica de manera efectiva debido a la ausencia de electrones libres en su estructura. Tienen
propiedades eléctricas y mecánicas específicas, como la permitividad y la rigidez dieléctrica.

Permitividad: La permitividad es una propiedad clave de los materiales dieléctricos que describe su
capacidad para polarizarse en respuesta a un campo eléctrico. Los materiales con alta permitividad
pueden almacenar más energía eléctrica en forma de carga eléctrica polarizada.

Polarización: Los materiales dieléctricos pueden polarizarse cuando se someten a un campo eléctrico,
lo que significa que sus dipolos eléctricos internos se alinean con el campo. Esto resulta en la
formación de una carga eléctrica neta en la superficie del material.

Rigidez Dieléctrica: La rigidez dieléctrica es la máxima intensidad de campo eléctrico que un material
dieléctrico puede soportar antes de experimentar una ruptura eléctrica. Es una propiedad importante
en la fabricación de dispositivos eléctricos y electrónicos.

Aplicaciones: Los materiales dieléctricos se utilizan en una amplia variedad de aplicaciones,

incluyendo condensadores, cables aislantes, aisladores eléctricos, dieléctricos en dispositivos
electrónicos, y en la fabricación de componentes eléctricos y electrónicos.

Pérdidas Dieléctricas: Los materiales dieléctricos pueden experimentar pérdidas de energía en forma
de calor debido a la resistencia interna en el material. Estas pérdidas se deben a la fricción entre los
dipolos eléctricos en el material y pueden ser un factor limitante en algunas aplicaciones.

Relación con la Teoría Electromagnética: Los materiales dieléctricos desempeñan un papel

importante en la teoría electromagnética, ya que afectan la propagación de ondas electromagnéticas,
como la reflexión y la refracción de la luz.

Selección de Materiales: La elección del material dieléctrico adecuado depende de la aplicación

específica y de las propiedades eléctricas requeridas. Es importante considerar la permitividad, la
rigidez y las pérdidas dieléctricas al seleccionar un material.
Desarrollo de Nuevos Materiales: La investigación continua se centra en el desarrollo de nuevos
materiales dieléctricos con propiedades mejoradas para aplicaciones avanzadas en tecnología y
electrónica.

En resumen, los materiales dieléctricos son esenciales en la tecnología moderna y la ingeniería

eléctrica, ya que desempeñan un papel crucial en la manipulación y el control de campos eléctricos y
son fundamentales en la fabricación de una amplia gama de dispositivos y sistemas eléctricos y
electrónicos.
 UNIVERSIDAD AUTONOMA DE BAJA CALIFORNIA

FACULTAD DE INGENIERIA Y TECNOLOGIA

VALLE DE LAS PALMAS

MATERIALES ELECTRICOS

PROFESOR: BENJAMIN GONZALEZ VIZCARRA

Actividad 12 El artículo se deberá de relacionarse con su carrera y la asignatura

GRUPO :539

PARRASALES TORRES PERLA YERALDINNE 01296999

Aislación de silicona en alta tensión

Este articulo nos habla sobre una nueva propuesta de la industria nacional:
seleccionador de alta tensión con aisladores de silicona. Donde en esta
propuesta se destacan dos aspectos: Por un lado, la silicona de los aisladores
reemplaza la porcelana y por otro lado la fabricación es totalmente nacional.
Tradicionalmente, los aisladores de los seccionadores que prestan servicio
en líneas y estaciones transformadoras de alta tensión se han construido con
porcelana, un material resistente y con muy buenas propiedades, tanto
eléctricas como mecánicas. Sin embargo, desde hace ya algunos años que
se viene observando en el mundo el reemplazo de ese material por silicona.

Ocurre que dicho polímero ofrece exactamente las mismas propiedades

eléctricas y mecánicas y, a la vez aporta las ventajas ya conocidas de este
tipo de material. Los aisladores de silicona son, sobre todo, mas livianos y
menos frágiles que los de porcelana. en consecuencia, tanto el montaje
como el transporte de los seccionadores se llevan a acabo de manera mucha
mas sencilla y en menor cantidad de tiempo, todo lo cual se traduce en una
importante reducción de costos.
Vale destacar que esta no es la primera vez que lago electromecánico
presenta alguno de sus modelos seleccionadores con aisladores de silicona.
En rigor la empresa cuenta con experiencia en el rubro: sus equipos siempre
aprobaron todos los ensayos y pruebas antes de su comercialización y
efectivamente ya han respondido de manera exitosa en aplicaciones reales,
incluyendo condiciones ambientales adversas como vientos fuertes,
humedad, nieve, lluvias torrenciales o polución del aire.
 UNIVERSIDAD AUTONOMA DE BAJA CALIFORNIA
FACULTAD DE INGENIERIA Y TECNOLOGIA
VALLE DE LAS PALMAS

METERIALES ELECTRICOS
PROFESOR BEJAMIN GONZALEZ VIZCARRA
RESUMEN

MATERIALES SEMICONDUCTORES

GRUPO :539
PARRASALES TORRES PERLA YERALDINNE 01296999
TIJUANA B.C, A 03 DE octubre de DEL 2023.
Los materiales semiconductores son una clase importante de materiales en la electrónica y
la tecnología moderna. Aquí tienes un resumen de los temas relacionados con los materiales
semiconductores:
Definición de semiconductores: Los semiconductores son materiales que tienen una
conductividad eléctrica intermedia entre los conductores (como metales) y los aislantes
(como cerámica). Esto significa que pueden conducir la electricidad bajo ciertas
condiciones.
Estructura atómica: Los semiconductores están compuestos por átomos que forman una
estructura cristalina. La forma en que estos átomos se organizan en el cristal afecta sus
propiedades eléctricas.
Comportamiento de los electrones: En un semiconductor, los electrones pueden moverse
entre órbitas energéticas, lo que los hace responsables de la conductividad eléctrica. Los
electrones en la banda de valencia están fuertemente ligados a los átomos, mientras que los
de la banda de conducción tienen mayor libertad de movimiento.
Gap de energía: Los semiconductores tienen un "gap de energía" o "band gap" entre la
banda de valencia y la banda de conducción. Este gap determina si un semiconductor es
tipo N o tipo P, y también influye en su conductividad.
Dopaje: Los semiconductores pueden ser dopados intencionadamente con impurezas para
cambiar sus propiedades eléctricas. El dopaje tipo N agrega electrones, mientras que el
dopaje tipo P agrega huecos electrónicos.
Juncción PN: La unión de un semiconductor dopado tipo N con uno tipo P crea una junta
PN. Esta es la base de muchos dispositivos electrónicos, como los diodos y los transistores.
Aplicaciones: Los semiconductores tienen una amplia gama de aplicaciones, desde
componentes electrónicos simples hasta microprocesadores avanzados. También se utilizan
en dispositivos optoelectrónicos como LEDs y fotodetectores.
Evolución tecnológica: La tecnología de semiconductores ha avanzado enormemente a lo
largo de los años, permitiendo dispositivos más pequeños, eficientes y poderosos. Esto ha
sido fundamental para el desarrollo de la electrónica moderna y la revolución de la
información.
Retos futuros: A medida que la tecnología avanza, surgen nuevos desafíos en la fabricación
de semiconductores, como la miniaturización y la gestión del calor. También se investiga en
nuevos materiales, como los semiconductores orgánicos, para expandir las posibilidades en
electrónica.
En resumen, los materiales semiconductores desempeñan un papel crucial en la electrónica
y la tecnología moderna, permitiendo una amplia gama de dispositivos y aplicaciones que
han transformado nuestra sociedad. Su capacidad de controlar y amplificar señales
eléctricas ha revolucionado la forma en que vivimos y nos comunicamos.
 UNIVERSIDAD AUTONOMA DE BAJA CALIFORNIA
FACULTAD DE INGENIERIA Y TECNOLOGIA
VALLE DE LAS PALMAS

METERIALES ELECTRICOS
PROFESOR BEJAMIN GONZALEZ VIZCARRA
RESUMEN

Materiales Magnéticos
GRUPO :539
PARRASALES TORRES PERLA YERALDINNE 01296999
TIJUANA B.C, A 13 DE octubre de DEL 2023.
Los materiales magnéticos son una categoría de materiales que exhiben propiedades
magnéticas, lo que significa que pueden interactuar con campos magnéticos y mostrar
comportamientos específicos. A continuación, se presenta un resumen de los temas
relacionados con los materiales magnéticos:
Magnetismo fundamental: El magnetismo es una propiedad de los materiales que se deriva
de la alineación de los espines de los electrones en un material. Los materiales magnéticos
pueden clasificarse en ferromagnéticos, antiferromagnéticos, ferrimagnéticos y
paramagnéticos, según cómo se dispongan los espines de los electrones.
Magnetización: La magnetización es el proceso por el cual un material se expone a un
campo magnético y se vuelve magnético. Los materiales ferromagnéticos son altamente
magnetizables y pueden mantener su magnetización incluso después de retirar el campo
magnético.
Curva de histéresis: La curva de histéresis es una representación gráfica de cómo cambia la
magnetización de un material en función del campo magnético aplicado. Esta curva es
característica de los materiales ferromagnéticos y muestra su capacidad para retener la
magnetización incluso en ausencia de un campo magnético externo
Aplicaciones prácticas: Los materiales magnéticos tienen numerosas aplicaciones en la vida
cotidiana y la industria. Estas aplicaciones incluyen imanes permanentes, transformadores,
motores eléctricos, discos duros, dispositivos electrónicos y equipos de resonancia
magnética nuclear (RMN).
Superconductividad: Algunos materiales magnéticos pueden volverse superconductores a
bajas temperaturas, lo que significa que conducen electricidad sin resistencia. La relación
entre el magnetismo y la superconductividad es un área de investigación importante en la
física de materiales.
Nanomateriales magnéticos: La nanotecnología ha permitido la fabricación de
nanomateriales magnéticos con propiedades únicas. Estos materiales tienen aplicaciones en
campos como la medicina (para la entrega de fármacos), la electrónica (en dispositivos de
almacenamiento de datos) y la tecnología de sensores.
Teoría del magnetismo: La teoría del magnetismo implica la comprensión de las
interacciones a nivel subatómico que conducen a la magnetización de los materiales. Esto
incluye conceptos como el espín de los electrones, el momento magnético y las fuerzas
magnéticas.

Tecnología de materiales magnéticos avanzados: La investigación en materiales magnéticos

continúa evolucionando, con un enfoque en el desarrollo de materiales con propiedades
magnéticas personalizables y controlables, lo que tiene implicaciones en la tecnología de
comunicaciones, almacenamiento de datos y dispositivos médicos.
En resumen, los materiales magnéticos desempeñan un papel fundamental en nuestra vida
cotidiana y en una amplia gama de aplicaciones tecnológicas. La comprensión de sus
propiedades y comportamientos magnéticos es esencial para su uso eficaz en diversos
campos.
 UNIVERSIDAD AUTONOMA DE BAJA CALIFORNIA
FACULTAD DE INGENIERIA Y TECNOLOGIA
VALLE DE LAS PALMAS

METERIALES ELECTRICOS
PROFESOR BEJAMIN GONZALEZ VIZCARRA
RESUMEN

“Difusión y soluciones sólidas”.

GRUPO :539
PARRASALES TORRES PERLA YERALDINNE 01296999

TIJUANA B.C, A 10 DE SEPTIEMBRE DEL 2023

Difusión en sólidos: La difusión se refiere al proceso de movimiento aleatorio de partículas en un
material desde áreas de alta concentración a áreas de baja concentración. En los sólidos, este
proceso es más lento que en los líquidos y los gases debido a la estructura cristalina.

Mecanismos de difusión: En sólidos, la difusión puede ocurrir a través de varios mecanismos, como
la difusión intersticial (átomos pequeños que se mueven entre los espacios vacíos en una estructura
cristalina) y la difusión de vacantes (átomos que se desplazan ocupando posiciones vacantes en la
estructura).

Soluciones sólidas: Una solución sólida es una mezcla homogénea de dos o más tipos de átomos,
iones o moléculas en un sólido. Estos solutos se incorporan en la red cristalina del solvente sólido
sin cambiar su estructura cristalina.

Solución sólida sustitucional: En este tipo de solución sólida, los átomos del soluto reemplazan
algunos de los átomos del solvente en su estructura cristalina, manteniendo la continuidad de la red
cristalina.

Solución sólida intersticial: En este tipo de solución sólida, los átomos del soluto se insertan en los
espacios intersticiales (huecos) entre los átomos del solvente en la estructura cristalina.

Soluciones sólidas no estequiométricas: Estas soluciones sólidas tienen una relación no

estequiométrica entre los solutos y los solventes. Esto puede conducir a propiedades interesantes y
variaciones en la conductividad eléctrica, la coloración, etc.

Diagramas de fase: Los diagramas de fase representan las condiciones de temperatura y

composición en las que existen diferentes fases sólidas y líquidas. La difusión y las soluciones
sólidas son esenciales para comprender la formación de fases en estos diagramas.

Aplicaciones tecnológicas: La comprensión de la difusión y las soluciones sólidas es fundamental

en una amplia gama de aplicaciones, como la fabricación de materiales avanzados, aleaciones
metálicas, semiconductores y cerámicas.

En resumen, la difusión y las soluciones sólidas son conceptos fundamentales en la ciencia de los
materiales y la física, que se relacionan con el movimiento de átomos y la mezcla de sustancias en
materiales sólidos. Estos conceptos son esenciales para comprender y desarrollar una variedad de
materiales y tecnologías en diversas industrias.
UNIVERSIDAD AUTONOMA DE BAJA CALIFORNIA
FACULTAD DE INGENIERIA Y TECNOLOGIA
VALLE DE LAS PALMAS

METERIALES ELECTRICOS

PROFESOR BEJAMIN GONZALEZ VIZCARRA

RESUMEN
“Propiedades eléctricas”.
GRUPO :539
PARRASALES TORRES PERLA YERALDINNE 01296999

TIJUANA B.C, A 24 DE SEPTIEMBRE DEL 2023

Las "Propiedades Eléctricas" son características fundamentales de los materiales y
componentes que afectan su comportamiento en relación con la electricidad.
Conductividad Eléctrica:
La conductividad eléctrica se refiere a la capacidad de un material para permitir el flujo de
corriente eléctrica a través de él.
Los metales suelen tener alta conductividad debido a la abundancia de electrones libres,
mientras que los aislantes tienen baja conductividad.
Resistencia Eléctrica:
La resistencia eléctrica es la propiedad que mide la oposición de un material al flujo de
corriente eléctrica.
Se mide en ohmios (Ω) y depende de factores como la longitud, el área transversal y la
temperatura del material.
Capacitancia:
La capacitancia es la capacidad de un componente, como un condensador, para almacenar
carga eléctrica.
Se mide en faradios (F) y depende de la geometría del condensador y del material dieléctrico
utilizado.
Inductancia:
La inductancia se refiere a la propiedad de oponerse a cambios en la corriente eléctrica y se
encuentra en componentes como bobinas y solenoides.
Se mide en henrios (H) y depende del número de vueltas del alambre y de las características
del núcleo magnético.
Permitividad y Permeabilidad:
La permitividad eléctrica se relaciona con la capacidad de un material para soportar un campo
eléctrico.
La permeabilidad magnética se refiere a la capacidad de un material para soportar un campo
magnético.
Ambas propiedades son esenciales en la electrónica, la ingeniería eléctrica y la ciencia de
materiales.
Superconductividad:
La superconductividad es una propiedad excepcional que permite que ciertos materiales
conduzcan corriente eléctrica sin resistencia a temperaturas extremadamente bajas.
Se utiliza en aplicaciones de alta tecnología, como la creación de imanes superconductores y
dispositivos de alta eficiencia.
Dieléctricos:
Los dieléctricos son materiales aislantes que se utilizan en condensadores para mejorar la
capacitancia al permitir la polarización bajo un campo eléctrico.
Ayudan a almacenar energía eléctrica en condensadores.

Estas propiedades eléctricas son fundamentales para comprender y diseñar dispositivos

eléctricos y electrónicos, sistemas de energía y circuitos, y desempeñan un papel crítico en
la ingeniería y la tecnología modernas.
 b o l e t í n d e l a s o c i e d a d e s p a ñ o l a d e c e r á m i c a y v i d r i o 6 2 (2 0 2 3) 468–478 469

mejoró la sinterización y las propiedades piezoeléctricas «duras» de KNN, aumentando los

valores de EC y Qm . La composición con x = 0,03 presentó la mayor permitividad a temper-
atura ambiente (εr  = 363) y las menores pérdidas dieléctricas (tan ı = 0,027). Además, fue la
muestra con los valores más altos de Qm y d33 , con Qm = 1.781 y d33 = 82 pC/N. Por tanto, esta
fue la mejor composición para obtener un material piezoeléctrico «duro» basado en KNN
dopado con Zr, lo que le convierte en un candidato prometedor para su uso como material
piezoeléctrico «duro» sin plomo en aplicaciones de alta potencia.
© 2023 Los Autores. Publicado por Elsevier España, S.L.U. en nombre de SECV. Este es un
artı́culo Open Access bajo la licencia CC BY (http://creativecommons.org/licenses/by/4.0/).

Several methods can be used to increase the densification

Introduction and piezoelectric properties of KNN, such as new processing
techniques like spark plasma sintering, hot press, solvother-
The most extensive and important piezoelectric composi-
mal synthesis and reactive templated grain growth. However,
tions, based on the lead zirconate titanate (Pb(Zr,Ti)O3 , PZT),
the cost of these techniques is relatively higher compared
contain more than 60 wt% of lead. Due to the high toxicity
to the conventional solid-state reaction method, and unsuit-
of lead to human health and the large number of environ-
able for practical application in industry. The other strategy to
mental regulations implemented to avoid contaminations, it
increase densification and improve the properties is to mod-
is essential to search for new piezoelectric materials. Lead-free
ify (Na,K)NbO3 ceramics using different aids and dopants such
ferroelectric materials have become very attractive from the
as CuO [2,13–15], ZnO [16–18], and K4 CuNb8 O23 [19,20], or dif-
standpoint of providing a solution to environmental problems.
ferent oxides [21,22], which are used to lower the sintering
Over the last decade, sodium potassium niobate (KNN)
temperature by forming a liquid phase during the sintering
based materials have attracted much attention among the
process. The lower sintering temperature will help to prevent
most promising candidates to replace lead-based piezoelectric
the loss of volatile elements like sodium.
materials. KNN is a solid solution of ferroelectric KNbO3 and
Furthermore, different authors have reported that the addi-
antiferroelectric NaNbO3 [1], showing a very high Curie tem-
tion of copper to KNN can provide typical characteristics of
perature (Tc = 420 ◦ C). However, the dielectric and piezoelectric
“hard” behaviour [7,13,19,23]. By adding these hardening ions
properties of pure KNN are relatively low (d33 = 80 pC/N)
to the perovskite (replacing Nb5+ by Cu2+ ions in the KNN
compared to that achieved with PZT-based compositions.
structure), oxygen vacancies are created, forming complex
Moreover, it is very difficult to obtain dense and well-sintered
defects, which act as pinning centres to hinder the motion
KNN ceramics by conventional solid-state sintering methods,
of the domain walls. This pinning effect of the domain walls
which makes it very difficult to replace the established PZT
lead to piezoelectric “hardening” effect [19,23]. Therefore, it is
with KNN.
interesting to explore the creation of oxygen vacancies in KNN
Since the publication of a paper by Saito et al. [2], where
systems.
high d33 ∼ 416 pC/N was obtained in textured KNN-based
Among other additives, zirconium is one of the dopants
ceramics due to its outstanding piezoelectric and ferroelec-
used to improve the density of KNN. Previous studies have
tric properties, numerous studies have been carried out using
shown that the addition of low zirconium oxide content dur-
this material [3,4], an early example of those being the Euro-
ing air sintering hampers the grain growth of K0.5 Na0.5 NbO3
pean project LEAF [5]. These lead-free materials are required to
ceramics [24]. According to the authors, the refinement of
replace PZT ceramics, for example, in high power applications,
the microstructure occurs because of two processes: at first,
such as transformers or ultrasonic motors, and high-intensity
the zirconia particles located in the grain matrix junctions
focused ultrasound driven by piezoelectric materials need
reduce the mobility of the grain boundaries, and second, the
“hard” piezoelectrics with a high mechanical quality factor
zirconium enrichment found in the grain boundary region pro-
(Qm ) and low dielectric loss to deliver high acoustic power
duces a defective structure that limits its mobility during the
without excessive heat generation and/or thermal runaway.
sintering process [24–26]. Further studies have shown that
For these applications, KNN-based material also seems to be
densification is improved by ZrO2 doping, however, it does
a promising candidate [1,3,4,6,7].
not prevent evaporation of alkali elements at high sintering
The preparation of dense ceramics based on (K,Na)NbO3
temperatures [27].
(KNN) depends strongly on the characteristics of the starting
Ramajo et al. [28] reported that the addition of ZrO2 causes
powder, methods of synthesis to ensure stoichiometric con-
an increase in the density and, as a consequence, in the elec-
trol, sintering temperature, etc. During the sintering process,
trical and dielectric properties. The authors determined that
it is difficult to achieve the ideal densification of pure KNN
zirconium changed the grain size and microstructure of KNN
ceramics due to the high volatility of K2 O and Na2 O and the
ceramics. In this case, some Zr4+ ions replace Nb5+ in B posi-
difficulty of sintering an elaborate body. Different studies were
tions of the perovskite lattice, while some ZrO2 particles are
conducted to analyse the dependence of the Na/K ratio on the
located at the grain boundaries. These ZrO2 particles at the
electrical properties of this material, as well as the optimum
grain boundary impede grain growth, improve the packing,
excess of these alkaline ions [8–12].
and increase the final density of the sample. A glassy phase
470 b o l e t í n d e l a s o c i e d a d e s p a ñ o l a d e c e r á m i c a y v i d r i o 6 2 (2 0 2 3) 468–478
was observed with increasing doping concentration. The addi-
tion of up to 1 mole% of Zr4+ produces a softening effect in the
ferroelectric properties and increases its density. The dielec-
tric and piezoelectric properties were reduced in samples with
higher contents of Zr4+ , more than 1 mole%.
Malic et al. [24] also reported that there is a change in the
microstructure of KNN ceramics with the addition of ZrO2
producing a more uniform microstructure and improving its
dielectric and piezoelectric properties. However, the improve-
ment of the piezoelectric constant (d33 = 100 pC/N) is limited
by the insertion of Zr to KNN.
Other authors [29] have also reported that the addition of
small amounts of Zr as acceptor dopant promotes densifica-
tion, resulting in an improvement in the functional properties
of KNN ceramics. A decrease in the Curie temperature and an
increase in the dielectric constant values were observed, and
an increase in the coercive field and remanent polarization
was also obtained in zirconium-doped KNN samples.
Different compositions with different Na/K ratios based
on the K1−x Nax NbO3 system have been reported to improve
the piezoelectric properties [3,4,7,8,12,14,16,19]. According to
all these studies on the Na/K ratio, it seems that the Na-
rich region exhibited higher piezoelectric properties than the
K-rich region. In particular, for the studies where zirconium
was used, most of the compositions explored were based on
K0.5 Na0.5 NbO3 . Therefore, in this work a study of the addi-
tion of ZrO2 to the composition K0.48 Na0.52 NbO3 (KNN) was
performed. K0.48 Na0.52 Nb1−x Zrx O3−ı (KNN-Zr) ceramics with
0 ≤ x ≤ 0.04 were prepared by solid-state reaction to investi-
gate the effect of zirconium on the structure, density, and the
electric and piezoelectric properties of KNN, as well as its rela-
tion with the effect of the creation of oxygen vacancies in the
KNN system.
Experimental procedure
Lead-free K0.48 Na0.52 Nb1−x Zrx O3−ı piezoelectric ceramics
where x = 0, 0.005, 0.015, 0.03 and 0.04 were prepared by the
conventional solid-state reaction method. Na2 CO3 (99.5%),
K2 CO3 (99%), Nb2 O5 (99.5%) and ZrO2 (99.5%) were used as
starting raw materials.
Two main problems can appear when it comes to keeping
the stoichiometry, in particular, the K+Na/Nb ratio: first,
the hygroscopic nature of alkaline carbonates, especially
potassium carbonate, and second, the high volatility of the
alkaline species at the processing temperature. Regarding
the first problem, different thermogravimetric studies [30,31]
have indicated that dehydration is completed at ∼200 ◦ C,
and therefore, the starting reagents were dried in an oven at
200 ◦ C for 24 h before use to avoid compositional errors when
weighing out the precursor mixture. The second problem
can be minimized or avoided if an alkaline carbonate excess
is added at the beginning of the synthesis and using closed
boats to sintered samples at high temperatures. Bomlai et al.
[32] observed that the addition of up to 5 mole% excess of
alkaline carbonates allowed milder calcination conditions
of the alkaline carbonate–niobium oxide powder mixture.
Therefore, based on this study, in this work, a 5 mole% excess
of alkaline carbonates was added to all KNN compositions
maintaining the K/Na ratio, and a closed Pt box was used
to minimize these problems. Platinum was used instead of
alumina boats to avoid any possible reaction and subsequent
contamination. The effect of this alkaline excess was studied
in KNN undoped and doped samples.
Dried powders of the reagents in each composition were
mixed in an agate planetary mill for 2 h in ethanol. The dried
powders were pressed into pellets of 13 mm in diameter and
fired at 850 ◦ C for 3.5 h. These pellets were then crushed and
milled again and were pressed into pellets 5 mm in diameter
and sintered at 1125 ◦ C for 2 h in an air atmosphere using a
closed box made from platinum foils and covering the pellets
with powders of the same composition. Binder was not used
to prepare the pellets. The bulk density of the ceramic samples
was measured by the Archimedes method.
X-ray powder diffraction (XRD) was recorded using a
Siemens D5000 diffractometer with CuK␣ radiation at room
temperature. Angle correction was carried out using an exter-
nal silicon standard.
Microstructure was evaluated by a field emission scanning
electron microscope, FE-SEM using a JEOL 7001F equipped
with a spectrometer for energy dispersion of X-ray analysis,
EDX, from Oxford instruments using an acceleration voltage
of 15 kV. For microstructural and microanalysis determination,
the samples were deposited on an Al holder and coated with
graphite.
Raman scattering spectra were recorded in the frequency
range of 90–1000 cm−1 at room temperature, using a modu-
lar Raman system from WITec GmbH, based on an automatic
vertical confocal microscope, model alpha300 apyron, with an
EMCCD ultra-high efficiency detector refrigerated at −60 ◦ C
and equipped with a 532 nm laser coupled to the microscope.
For the electrical properties measurements of the pellets
sintered at 1125 ◦ C Pt paste electrodes were placed on oppo-
site faces. The paste was dried, decomposed, and hardened
by gradually heating up to 900 ◦ C and at this temperature was
maintained for 2 h. The pellets with attached electrodes were
placed in a conductivity jig and the impedance data were
recorded from room temperature to 900 ◦ C using a Hewlett
Packard 4192A analyser over the frequency range from 5 Hz
to 13 MHz. The data obtained were corrected concerning the
pellet geometry and also the cell blank capacitance (“jig cor-
rection”). Fixed frequency capacitance measurements were
made using an LCR impedance meter over the room tem-
perature range up to 500 ◦ C with data recorded at various
frequencies between 5 and 100 kHz.
Polarization versus electric field (P–E) hysteresis loops
were carried out in a dielectric liquid bath (FC40, 3MTM
FluorinertTM ) at room temperature. Low-frequency (0.1 Hz)
and high-voltage sine waves were applied combining a syn-
thesizer/function generator (HP3325B, Hewlett-Packard Inc.,
Palo Alto, CA) and a high-voltage amplifier (Trek model 10/40A,
Medina, NY). Several consecutive high-voltage cycles (4–5
cycles) were performed to ensure a stable switching behaviour
for each measurement (i.e., for each applied electric field).
For the piezoelectric parameters’ measurements, the sam-
ples were immersed in a silicone oil bath at 80 ◦ C for 30 min
under 30 kV/cm. Subsequently, the piezoelectric constant
d33 was measured using a piezo-d33 meter (YE2730A, APC
International) at room temperature. The electromechanical
coupling factor, kp and the mechanical quality factor, Qm
 b o l e t í n d e l a s o c i e d a d e s p a ñ o l a d e c e r á m i c a y v i d r i o 6 2 (2 0 2 3) 468–478 471

respectively. The main phase detected in both samples is

Fig. 1 – XRD patterns of: (a) undoped KNN simple without (i)
and with (ii) 5 mole% excess of alkaline cations; (b) pure
and Zr-doped KNN ceramics. Inset in (b): magnificated
patterns in the 22–23◦ 2 range.
were also determined at room temperature by the reso-
nance/antiresonance method based on the IEEE standards.
Results and discussion
Fig. 1(a) shows the XRD patterns of the undoped KNN with-
out and with an excess of alkaline carbonates at 1125 ◦ C,
perovskite, but a secondary phase was detected for KNN
without any excess of alkaline ions. The peaks of the sec-
ondary phase were assigned to KNbO3 (JCPDS-ICDD 32-0822)
and it could be due to slight changes in the stoichiometric
ratio caused by highly volatile alkaline elements during the
sintering process. Therefore, a 5 mole% excess of alkaline
ions was used in all samples, allowing for the preparation of
single-phase perovskite.
The XRD patterns of the KNN-based ceramics doped with
different amounts of zirconium (x = 0–0.04) and sintered at
1125 ◦ C for 2 h are shown in Fig. 1(b). For compositions below
x = 0.04, a single-phase perovskite structure is observed, and
therefore, an aliovalent substitution of zirconium at B-sites of
KNN was formed below this composition. A secondary phase
assigned to ZrO2 (JCPDS-ICDD 88-2390) appeared at high zir-
conium concentration. In comparison to the results obtained
by Ramajo et al. [28], using the reagents and the synthesis
method described previously, no secondary phase formation
was observed at low dopant concentrations, indicating that
the processing parameters are relevant factors to be consid-
ered.
Inset of Fig. 1(b) shows the XRD patterns in the 2 range
of 22–23◦ needed to assign the correct polymorph of the per-
ovskite phase in each case. Samples with x = 0 and 0.005
exhibit a single-phase perovskite structure with orthorhombic
symmetry (Cm2m space group) which can be indexed accord-
ing to JCPDS-ICDD card no. 32-0822 (KNbO3 ). When the amount
of zirconium is increased, there seems to be an evolution of the
crystalline phase to a monoclinic phase and peaks can also be
indexed to a monoclinic perovskite structure with symmetry
of space group Pm, according to the JCPDS-ICDD no. 74-2025
(Na0.9 K0.1 NbO3 ). Note that it is difficult to ascertain the current
symmetry of this phase with the XRD data present, however,
the phase changes can be suggested by the changes in sym-
metry of the (1 0 0) and (0 0 1) peaks of the orthorhombic phase
(blue lines) to the (2 0 0) and (0 2 0) peaks of the monoclinic
phase (red lines) in the 2 range of 22–23◦ shown in this figure.
As can be observed, the main phase for x = 0.04 seems to be
monoclinic. Note that the theoretical peaks represented with
lines are displaced from the position of theoretical patterns.
The small displacements observed in the diffraction peaks
are due to the possible difference in the Na and K content,
and the replacement of Zr by Nb in the nominal composition
represented in the theoretical diffraction pattern.
SEM images for the surface of sintered samples with x = 0
and x = 0.03 are shown in Fig. 2(a) and (b). All of the samples
have the characteristic morphology of alkaline niobate ceram-
ics. These samples, as well as the others (not shown), exhibited

Table 1 – Relative density (Arquimedes’ method), relative permittivity εr  , dielectric loses tan ı, piezoelectric coefficient
d33 , electromechanical coupling factor kp and mechanical quality factor Qm at room temperature.
Composition relative (%) εr  (100 kHz) tan ı (100 kHz) d33 (pC/N) kp (%) Qm

x=0 86.9 375 0.079 150 31 630

x = 0.005 92.5 252 0.036 46 30 1152
x = 0.015 91.2 284 0.079 48 29 1346
x = 0.030 89.9 363 0.027 82 30 1781
x = 0.040 90.0 326 0.028 60 30 901
472 b o l e t í n d e l a s o c i e d a d e s p a ñ o l a d e c e r á m i c a y v i d r i o 6 2 (2 0 2 3) 468–478
Fig. 2 – SEM of the pellet surface for x = 0 (a) and x = 0.03 (b)
with a 5 mole% of alkaline cation excess. (c) K/Na molar
ratio from EDX analysis as a function of x for samples with
an excess of alkaline ions.
the formation of a glassy phase (indicated with arrows in
Fig. 2(b)). It has also been observed that, the higher the addi-
tive amount of zirconium is, the greater the glassy phase is.
Other authors [21,26] also have observed this influence of the
microstructure when ZrO2 was added to KNN. The relative
density of the ceramic samples is shown in Table 1 for each
composition. The incorporation of zirconium improved the
density of the samples.
No evidence of secondary phases was observed by EDX
analysis for samples with x < 0.04, which is supported by
the XRD results. Fig. 2(c) shows the K/Na molar ratio ver-
sus the amount of Zr in each composition. The K/Na ratio
reached an almost constant value independent of the amount
of zirconium. Therefore, the excess of alkali ions makes it
possible to obtain compositions close to the nominal one.
The EDX analysis showed that the atomic percentages of the
elements differ from the nominal composition. All composi-
tions have a K/Na ratio higher than the nominal composition
(K/Na = 0.923), indicating that a greater loss of Na is produced
during the calcination process, which is more evident for the
undoped composition.
Raman spectroscopy has been used to demonstrate the
nature of crystal symmetry in the different compositions as a
function of Zr dopant, giving information about the structural
deformation of perovskite caused by both tilt and cation dis-
placement of the BO6 octahedron on a local scale. Fig. 3 shows
the Raman spectra of pure and Zr-doped KNN ceramics at
room temperature, where the typical vibrations corresponding
to the perovskite phase and associated with the BO6 octahedra
are present [33–35]. According to group theory, the main vibra-
tions are the 1A1g (1 ) + 1Eg (2 ) + 2F1u (3 , 4 ) + F2g (5 ) + F2u (6 )
modes. The stretching modes are 1A1g (1 ) + 1Eg (2 ) + 1F1u (3 )
and the others are bending modes [33]. A1g (1 ) and F2g (5 ) are
detected as fairly intense bands in systems like KNN due to
their almost ideal octahedral equilateral symmetry. Therefore,
in this structure, the main vibrations are usually related to the
NbO6 -octahedron [34]. The vibrational modes are indicated in
this figure. The peaks located between 100 and 160 cm−1 can
be associated with translational modes of alkaline niobates
K+ /Na+ and rotational modes of the NbO6 -octahedron [35]. The
F2u (6 ) mode of NbO6 -octahedra is possibly overlapped, and
thus is not evidently seen; nevertheless, it is labelled in Fig. 3.
As shown in Fig. 3(a), to obtain statistical reliability, 50
Raman spectra (collected over an area of 70 ␮m × 70 ␮m) were
composed for each sample, keeping the measurement condi-
tions constant. It is possible to note that the intensity of the
bands due to the vibrations of the NbO6 -octahedra increases
as the zirconium content increases. Moreover, the A1g (1 )
mode shifts to lower frequencies as well as the F2g (5 ) mode.
A possible explanation for this is the presence of oxygen
vacancies, which cause a decrease in the bond strength. The
intensity of the Raman band also depends on the structure
of the sample, surface roughness, and density of the material
[35]. As commented in the introduction of the manuscript,
zirconium can improve the density of KNN ceramics, although
regarding the results obtained in our samples, there is no
significant change in density when x is larger than 0.005
(Table 1). In addition, the changes in roughness on the surface
of the sample observed in the SEM images could be neglected.
 b o l e t í n d e l a s o c i e d a d e s p a ñ o l a d e c e r á m i c a y v i d r i o 6 2 (2 0 2 3) 468–478
Fig. 3 – (a) Raman spectra corresponding to undoped and
Zr-doped KNN collected at room temperature. Variation of
(b) spectral band position and (c) FWHM of the A1g (1 )
stretching mode for Zr-doped KNN ceramics as a function
of x. The standard deviation is shown in the inset of each
figure.
Therefore, the changes in Raman band intensity that were
observed here should be primarily dependent on sample
structure dissimilarities. Furthermore, according to XRD, there
seems to be a phase change when the amount of zirconium
increases which can be confirmed by this hypothesis.
473
Fig. 4 – Relative permittivity as a function of temperature at
100 kHz. Inset: variation of TC and TO–T as a function of
composition for Zr-doped KNN samples.
According to Zhu and co-workers [35], the Raman intensity
characterizes the differentiated frequency-dependent polariz-
ability concerning nuclear displacements, and consequently,
the scattering intensity is determined by the amount of
change in the polarizability. In this case, the Nb5+ ion is sub-
stituted by a Zr4+ ion with higher ionic radius (r(Nb5+ )CN=6 = 78
pm and r(Zr4+ )CN=6 = 86 pm). Therefore, the lattice distortion
due to Zr insertion, which changes the polarizability of the
O–Nb–O vibration in the NbO6 -octahedra. To avoid the pos-
sibility of particle orientation effects on the measured band
intensity, were collected a representative amount of Raman
spectra in all samples.
Fig. 3(b) and (c) shows the deviation of the spectral band
position and full width at half maximum (FWHM) of the A1g
mode (1 ) for the Zr-doped KNN as a function of x, respectively.
The dispersion of the adjusted values for the selected vibration
mode is also shown inserted in these figures. These figures
show that as x increases, the band representing the A1g (1 )
stretching mode clearly shifts towards lower wavenumbers
while being simultaneously broadened. The larger dispersion
of the Raman band position is also expected for samples pre-
senting different phases, and it is found when x is equal to
0.03.
From the XRD and Raman results, it can be assumed that
the orthorhombic (O) to the monoclinic (M) phase transition
has already started occurring in the sample with x = 0.03.
Therefore, the Raman results confirmed the XRD results,
showing the coexistence of O and M phases for x = 0.03, which
suggests a change in structure/phase of the samples with
increasing x.
Fig. 4 exhibits the relative permittivity against the temper-
ature of the Zr-doped KNN ceramics, measured at 100 kHz
in the temperature range from 25 ◦ C to 500 ◦ C, for sam-
ples sintered at 1125 ◦ C for 2 h. Permittivity profiles are
frequency-independent and show two maxima, one around
200 ◦ C associated with the orthorhombic to the tetragonal
phase transition, or the monoclinic to the tetragonal phase
transition for x = 0.04, and the other at high temperatures,
474 b o l e t í n d e l a s o c i e d a d e s p a ñ o l a d e c e r á m i c a y v i d r i o 6 2 (2 0 2 3) 468–478

which is associated with the tetragonal ferroelectric to the

cubic paraelectric phase transition. In Zr-doped KNN samples,
the tetragonal-to-cubic (T–C) phase transition shifts towards
lower temperatures, whereas the orthorhombic/monoclinic-
to-tetragonal (O/M–T) phase transition remains almost
constant. Moreover, a typical normal ferroelectric to paraelec-
tric phase transition is observed for undoped KNN showing
a narrow phase transition with high permittivity. However,
this transition broadens and the permittivity value decreases
on doping, suggesting the appearance of diffuse phase tran-
sition, probably caused by local fluctuations induced by the
incorporation of Zr4+ ions into the crystalline lattice.
The temperatures of the permittivity maxima, which are
taken to represent the orthorhombic/monoclinic to tetragonal
phase (TO/M–T ) and the tetragonal to cubic phase (TC ) transition
temperature, are shown in the inset of Fig. 4 as a function of x.
A gradual decrease is observed in the TC with x from approxi-
mately 410 ◦ C for x = 0, to approximately 330 ◦ C for x = 0.04. The
decrease in TC can be explained by assuming that zirconium is
being introduced into the perovskite structure. This tempera-
ture change for Zr-doped samples may also be a consequence
of the acceptor doping effect [29]. The values of the relative
permittivity and tan ı at room temperature and at 100 kHz are
shown in Table 1 for all compositions. The highest εr  value
and the lowest dielectric loss were observed for the sample
with x = 0.03.
To characterize the electrical properties of the sam-
ples, variable frequency impedance measurements were
performed on pellets sintered in air and slowly cooled to room
temperature by switching off the furnace. A selection of typ-
ical impedance data is represented in Fig. 5 and S1 and S2
of the Supplementary Information (SI) for pellets sintered at
1125 ◦ C. Fig. 5(a) shows an almost semicircular arc with distor-
tion from the ideal semicircular shape at low frequencies in Fig. 5 – (a and b) Impedance complex plane plot, Z*, for x = 0
the impedance complex plane plot for the undoped KNN sam- and x = 0.03 samples at 743 ◦ C and 756 ◦ C, respectively. Inset
ple. Z /M spectroscopic plots (Fig. S2(a) of SI) showed a single in (a and b): spectroscopic plots of capacitance for both
peak in each spectrum with similar peak maximum frequen- samples at the same temperature.
cies. Since low capacitance bulk effects dominate the electric
modulus (M spectra), the data in this figure suggest that the
sample’s main resistive component is related to the sample
bulk, with a capacitance of approximately 3.5 × 10−11 F cm−1 10−7 F cm−1 and is attributed to the sample–electrode interface
at 743 ◦ C, as shown in the inset of Fig. 5(a). The low-frequency [36]. Therefore, this electrical inhomogeneity, in particular the
resistance is associated with the sample–electrode contact. appearance of grain boundaries when doping with Zr, could
For the Zr-doped samples, another electrical compo- influence the final piezoelectric properties. The presence of
nent became apparent and therefore, the electrical response defects in the structure generated when Zr replaces Nb in the
started to be inhomogeneous. A similar impedance response KNN, could be located at the grain boundaries and it could
was observed for all samples, Fig. 5(b) and S1(b) and S2(b)–(d) influence to the motion of ferroelectric domains, which can
of the SI. Two arcs are apparent in the impedance complex in turn affect the piezoelectric characteristics. However, given
plane plot, Fig. 5(b) and S1 of the SI: a high-frequency arc the different interpretations in the literature [37–40], pinpoint-
of resistance R1 and a large-intermediate-frequency arc of ing the exact location of these defects would require more
resistance, R2 . Both dominated the total resistance (R1 + R2 ). detailed studies.
At high temperatures and low frequencies, a low resistance From impedance data such as those shown in Fig. 5,
appeared, and it is associated with the sample–electrode con- resistance values for the bulk, R1 , and grain boundary, R2 ,
tact. Two peaks also appeared in the Z /M spectroscopic plots, components were extracted and are presented as Arrhenius
Fig. S2(b)–(d), and two frequency-independent plateaus were plots of log  vs T−1 in Fig. 6(a) and (b), respectively. All
observed in the spectroscopic plots of capacitance, inset of data represent highly insulating samples, with the complete
Fig. 5(b) and S1 of the SI, with values around 2–3 × 10−11 F cm−1 absence of any semiconducting component. The activation
and 1–2 × 10−9 F cm−1 , which are attributed to a conventional energies were ∼0.75 to 1.4 eV for both bulk and grain bound-
bulk and grain boundary, respectively. At the highest tempera- ary. The grain boundary conductivity,  2 , increases when the
tures and lowest frequencies, the capacitance rises to values of zirconium concentration increases, reaching the maximum
 b o l e t í n d e l a s o c i e d a d e s p a ñ o l a d e c e r á m i c a y v i d r i o 6 2 (2 0 2 3) 468–478
Fig. 6 – Arrhenius plots for the bulk (a) and grain boundary
(b) conductivity for pure KNN and Zr-doped KNN ceramics.
values of conductivity for the sample with x = 0.03. There is
also a change in slope when the Zr content increases from
x = 0.005–0.015. However, the bulk conductivity,  1 , remains
almost the same and a slight decrease when an increase in the
zirconium concentration is observed. This unusual behaviour
may be attributed to a non-uniform distribution of the Zr
dopant between the grain and the grain boundary since the
presence of ZrO2 inclusions in our samples was not observed
by XRD, Raman, or SEM/EDX.
Therefore, two main effects were observed in the Zr-doped
samples. The first is that the conductivity of both components
increases in comparison to the x = 0 sample probably due to the
presence of the oxygen vacancies. The second is that the effect
475
Fig. 7 – (a) P–E hysteresis loops of the pure KNN and
Zr-doped KNN ceramics measured at 0.1 Hz at room
temperature. (b) Evolution of the piezoelectric parameters
(Pr and Ec ) with x in Zr-doped KNN ceramics.
of the oxygen defect is higher in the grain boundary region,
the most conductive composition being that with x = 0.03. This
defect in the structure in the grain boundary region may be
related to the limitation of KNN grain growth. The effect of
the adding acceptor dopants, inhibiting the grain growth, and
also causing the formation of abnormally grown grains has
also been observed by other authors [24,26].
Thus, the change in electrical response from pure KNN to
Zr-doped samples could be attributed to the change in the
oxygen content. The impedance data are very sensitive to vari-
ation in the oxygen content of the sample, and therefore, when
samples are Zr-doped, oxygen vacancies are created, and the
oxygen content is different.
The ferroelectric hysteresis loops (P–E) for the pure KNN
and Zr-doped samples measured at 0.1 Hz and at room tem-
perature are shown in Fig. 7(a), and the remanent polarization
(Pr ) and coercive field (Ec ) values are represented in Fig. 7(b)
476 b o l e t í n d e l a s o c i e d a d e s p a ñ o l a d e c e r á m i c a y v i d r i o 6 2 (2 0 2 3) 468–478
as a function of x. In KNN-based ceramics doped with dif-
ferent amounts of zirconium, a dramatic increase in the
coercive field is observed. This increase in Ec suggests that
the material becomes harder which is consistent with the
hypothesis that oxygen vacancies are formed. A small amount
of zirconium (x = 0.005) leads to a hysteresis loop typical of a
ferroelectric material. Ceramics with higher Zr concentration
(x > 0.005) show loops that are not fully saturated. Therefore, a
higher electric field must be applied to obtain well-saturated
hysteresis loops. This behaviour can also be attributed to
the conductivity associated with the presence of the oxygen
vacancies, especially in the grain boundary region.
The change in piezoelectric coefficient d33 , electromechan-
ical coupling factor, kp , and mechanical quality factor, Qm , are
shown in Table 1. The d33 value for pure KNN is 150 pC/N,
which is close to that reported by Dai et al. [41] for the same
composition and higher than that described by Hu et al.
[42]. In all Zr-doped KNN ceramics, the piezoelectric coeffi-
cient, d33 , decreases with respect to pure KNN. Significant
changes in the electromechanical coupling factor, kp , are not
observed between pure KNN and doped ceramics. In contrast,
the mechanical quality factor Qm of Zr-doped KNN ceram-
ics (x = 0.005, 0.015 and 0.03) is higher than that of pure KNN.
This increase can be explained in terms of the incorporation
of zirconium into the lattice and the generation of oxygen
vacancies. Oxygen vacancies produced by replacement have a
pinning effect for the motion of ferroelectric domains, which
can make the material become hard.
The composition with x = 0.03 presented the highest per-
mittivity at room temperature, and the lowest dielectric losses.
Moreover, it was the sample with the highest Qm and d33 val-
ues, much higher even than undoped KNN in the case of Qm .
It is important to note that this composition has a mixture
of orthorhombic and monoclinic phases. Therefore, we can
conclude that it is the best composition to obtain a “hard”
piezoelectric material based on zirconium-doped KNN and it
would be a promising candidate for high power applications.
Conclusions
Lead-free “hard” piezoelectric ceramics based on
K0.48 Na0.52 Nb1−x Zrx O3 were prepared by the conventional
mixed oxide method. Based on XRD and Raman results,
when the amount of zirconium was increased there was an
evolution of the crystalline phase from the orthorhombic to
the monoclinic phase, showing a mixture of both crystalline
phases at intermediate compositions. Therefore, composi-
tions close to the orthorhombic-monoclinic phase boundary
were prepared. The final density increased when zirconium
is present in the KNN and the formation of a glassy phase is
observed.
The addition of Zr was effective in improving the sin-
terability and the “hard” piezoelectric properties of KNN,
increasing the Ec and Qm values. The composition with x = 0.03
(K0.48 Na0.52 Nb0.97 Zr0.03 O3 ) presented the highest permittivity
at room temperature, and the lowest dielectric losses. More-
over, it was the sample with the highest Qm and d33 values,
which were even much higher than undoped KNN in the case
of the Qm . Therefore, it is the best compositions with which
to obtain a “hard” piezoelectric material based on zirconium-
doped KNN, thus making it a promising candidate to be used
as “hard” lead-free piezoelectric material for high power appli-
cations.
Acknowledgements
H.B.-M. and E.C. thank the Universitat Jaume I
[UJI-B2019-41] and Spanish Ministerio de Ciencia e
Innovación [Grant PID2020-116149GB-I00 funded by
MCIN/AEI/10.13039/501100011033] for the financial support.
E.L.S.V. thanks the Generalitat Valenciana [GRISO-
LIA/2019/054] for the predoctoral contract. X.V. is a Serra
Húnter Lecturer Fellow and is grateful to the Generalitat
de Catalunya. This research did not receive any specific
grant from funding agencies in the public, commercial, or
not-for-profit sectors.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.bsecv.2022.12.001
references
[1] T.R. Shrout, S.J. Zhang, Lead-free piezoelectric ceramics:
alternatives for PZT, J. Electroceram. 19 (2007) 113–126,
http://dx.doi.org/10.1007/s10832-007-9047-0.
[2] Y. Saito, H. Takao, T. Tani, T. Nonoyama, K. Takatori, T.
Homma, T. Nagaya, M. Nakamura, Lead-free piezoceramics,
Nature 432 (2004) 84–87,
http://dx.doi.org/10.1038/nature03028.
[3] M.E. Villafuerte-Castrejón, E. Morán, A. Reyes-Montero, R.
Vivar-Ocampo, J.-A. Peña-Jiménez, S.-O. Rea-López, L. Pardo,
Towards lead-free piezoceramics: facing a synthesis
challenge, Materials 9 (2016) 21–27,
http://dx.doi.org/10.3390/ma9010021.
[4] S. Garroni, N. Senes, A. Iacomini, S. Enzo, G. Mulas, L. Pardo,
S. Cuesta-Lopez, Advanced synthesis on lead-free
Kx Na(1−x) NbO3 piezoceramics for medical imaging
applications, Phys. Stat. Sol. A 215 (2018),
http://dx.doi.org/10.1002/pssa.201700896, 1700896-1-15.
[5] E. Ringgaard, T. Wurlitzer, Lead-free piezoceramics based on
alkali niobates, J. Eur. Ceram. Soc. 25 (2005) 2701–2706,
http://dx.doi.org/10.1016/j.jeurceramsoc.2005.03.126.
[6] J.B. Lim, Chapter 2: Modified-(K,Na)NbO3 piezoelectric
ceramics for ‘hard’ lead-free materials in: J.J. Roa and M.
Segarra (Eds.), Recent advances in ceramic materials
Research (Material Science and Technology), Ed. Nova
Science Pub. Inc., UK (2013) 31-50. ISBN 1624177298.
[7] J.B. Lim, S. Zhang, J.H. Jeon, T.R. Shrout, (K,Na)NbO3 -based
ceramics for piezoelectric “hard” lead-free materials, J. Am.
Ceram. Soc. 1220 (2010) 2009–2011,
http://dx.doi.org/10.1111/j.1551-2916.2009.03528.x.
[8] H. Du, S. Qu, Z. Xu, X. Wei, W. Zhou, D. Zhu, L. Fa, Na/K ratios
dependence of piezoelectric and ferroelectric properties in
(K1−x Nax )NbO3 lead-free ceramics, J. Adv. Dielect. 1 (2011)
471–478, http://dx.doi.org/10.1142/S2010135X11000598.
[9] H. Birol, D. Damjanovic, N. Setter, Preparation and
characterization of (K0.5 Na0.5 )NbO3 ceramics, J. Eur. Ceram.
Soc. 26 (2006) 861–866,
http://dx.doi.org/10.1016/j.jeurceramsoc.2004.11.022.
 b o l e t í n d e l a s o c i e d a d e s p a ñ o l a d e c e r á m i c a y v i d r i o 6 2 (2 0 2 3) 468–478
[10] Y. Chang, Z. Yang, X. Chao, R. Zhang, X. Li, Dielectric,
piezoelectric properties of alkaline-earth titanate doped
(K0.5 Na0.5 )NbO3 ceramics, Mater. Lett. 61 (2007) 785–789,
http://dx.doi.org/10.1016/j.matlet.2006.05.065.
[11] J.F. Li, K. Wang, F.Y. Zhu, L.Q. Cheng, F.Z. Yao,
(K,Na)NbO3 -based lead-free piezoceramics: fundamental
aspects, processing technologies and remaining challenges,
J. Am. Ceram. Soc. 96 (2013) 3677–3696,
http://dx.doi.org/10.1111/jace.12715.
[12] R. Sumang, C. Wicheanrat, T. Bongkarn, S. Maensiri, High
densification and dielectric properties of lead-free
(K0.5 Na0.5 )NbO3 piezoelectric ceramics with optimum excess
Na2 O and K2 O contents, Ceram. Int. 41 (2015) S136–S142,
http://dx.doi.org/10.1016/j.ceramint.2015.03.228.
[13] E. Li, H. Kakemoto, S. Wada, T. Tsurumi, Influence of the CuO
on the strucutre and piezoelectic properties of the alkaline
niobate-based lead free ceramics, J. Am. Ceram. Soc. 90
(2007) 1787–1791,
http://dx.doi.org/10.1111/j.1551-2916.2006.01465.x.
[14] H. Takao, Y. Saito, Y. Aoki, K. Hiribuchi, Microstructural
evolution of crystalline-oriented (K0.5 Na0.5 )NbO3
piezoelectric ceramics with a sintering aid of CuO, J. Am.
Ceram. Soc. 89 (2006) 1951–1956,
http://dx.doi.org/10.1111/j.1551-2916.2006.01042.x.
[15] H. Ahmadimoghadam, M.D. Chermahini, High remnat
polarization of (K0.5 Na0.5 )0.99 (Ba0.0025 Sr0.0025 )NbO3
piezoceramics with nano-CuO sintering aid, Appl. Phys. A
127 (2021) 620, http://dx.doi.org/10.1007/s00339-021-04773-6.
[16] F. Rubio-Marcos, M.G. Navarro-Rojero, J.J. Romero, J.F.
Fernandez, Effect of ZnO on the structure, microestructure
and electric properties of KNN-modified piezoceramics, J.
Eur. Ceram. Soc. 29 (2009) 3045–3052,
http://dx.doi.org/10.1016/j.jeurceramsoc.2009.04.026.
[17] R. Hayati, A. Barzegar, Microstructure and electrical
properties of lead free potassium sodium niobate
piezoceramics with nano ZnO additive, Mater. Sci. Eng. B 172
(2010) 121–126, http://dx.doi.org/10.1016/j.mseb.2010.04.033.
[18] A. Li, L. Tan, X. Wang, W. Zhu, Y. Wang, Improved electrical
properties of potasium-sodium niobate piezoceramics owing
to micro-sized non-uniform structure, J. Alloys Comp. 889
(2021) 161688,
http://dx.doi.org/10.1016/j.jallcom.2021.161688.
[19] S. Zhang, J.B. Lim, T.R. Shrout, Characterization of hard
piezoelectric lead-free ceramics, IEEE Trans. Ultrason.
Ferroelectr. Freq. Control 58 (2009) 1523–1527,
http://dx.doi.org/10.1109/TUFFC.2009.1215.
[20] S. Priya, S. Nahm, Leas-free Piezoelectrics, Springer, New
York, 2012, pp. 209–251.
[21] Y. Chen, J. Xing, T. Wang, F. Wang, R. Li, X. Sun, L. Xie, Z. Tan,
J. Zhu, Realization of densified microstructure and large
piezoelectricity in KNN ceramics via the addition of oxide
additives, J. Mater. Sci. Mater. Electron. 32 (2021)
20211–20224, http://dx.doi.org/10.1007/s10854-021-06525-x.
[22] R. Zuo, J. Rödel, R. Chen, L. Li, Sintering and electrical
properties of lead-free Na0.5 K0.5 NbO3 piezoelectric ceramics,
J. Am. Ceram. Soc. 89 (2006) 2010–2015,
http://dx.doi.org/10.1111/j.1551-2916.2006.00991.x.
[23] M. Matsubara, T. Yamaguchi, K. Kikuta, S.I. Hirano,
Sinterability and piezoelectric properties of (K,Na)NbO3
ceramics with novel sintering aid, Jpn. J. Appl. Phys. 43 (2004)
7159–7163, http://dx.doi.org/10.1143/JJAP.43.7159.
[24] B. Malic, J. Bernard, A. Bencan, M. Kosec, Influence of
zirconia addition on the microstructure of K0.5 Na0.5 NbO3
ceramics, J. Eur. Ceram. Soc. 28 (2008) 1191–1196,
http://dx.doi.org/10.1016/j.jeurceramsoc.2007.11.004.
[25] B. Malic, A. Bencan, T. Rojac, M. Kosec, Lead-free
piezoelectrics based on alkaline niobates: synthesis,
477
sintering and microstructure, Acta Chim. Slov. 55 (2008)
719–726.
[26] X. Wang, J. Wun, X. Chem, B. Zhang, J. Zhu, D. Xiao,
Compositional dependence of phase structure and electrical
properties in (K0.50 Na0.50 )0.97 Bi0.01 (Nb1−x Zrx )O3 lead-free
ceramics, Ceram. Int. 39 (2013) 8021–8024,
http://dx.doi.org/10.1016/j.ceramint.2013.03.071.
[27] G. Lévêque, P. Marchet, F. Levassort, L.P. Tran-Huu-Hue, J.R.
Duclere, Lead free (Li,Na,K)(Nb,Ta,Sb)O3 piezoelectric
ceramics: influence of sintering atmosphere and ZrO2
doping on densification, microstructure and piezoelectric
properties, J. Eur. Ceram. Soc. 31 (2011) 577–588,
http://dx.doi.org/10.1016/j.jeurceramsoc.2010.10.031.
[28] L. Ramajo, J. Taub, M.S. Castro, Influence of zirconium
addition on final properties of K0.5 Na0.5 NbO3 -based ceramics,
J. Mater. Sci. Mater. Electron. 25 (2013) 168–173,
http://dx.doi.org/10.1007/s10854-013-1568-5.
[29] X. Vendrell, J.E. Garcia, X. Bril, D.A. Ochoa, L. Mestres, G.
Dezanneau, Improving the functional properties of
(K0.5 Na0.5 )NbO3 piezoceramics by acceptor doping, J. Eur.
Ceram. Soc. 35 (2015) 125–130,
http://dx.doi.org/10.1016/j.jeurceramsoc.2014.08.033.
[30] T. Rojac, M. Kosec, P. Segedin, B. Malic, J. Holc, The formation
of a carbonato complex during the mechanochemical
treatment of a Na2 CO3 –Nb2 O5 mixture, Solid State Ion. 177
(2006) 2987–2995, http://dx.doi.org/10.1016/j.ssi.2006.08.001.
[31] P.K. Heda, D. Dollimore, K.S. Alexander, D. Chen, E. Law, P.
Bicknell, A method of assessing solid state reactivity
illustrated by thermal decomposition experiments on
sodium bicarbonate, Thermochim. Acta 255 (1995) 255–272,
http://dx.doi.org/10.1016/0040-6031(94)02154-g.
[32] P. Bomlai, P. Wichianrat, S. Muensit, S.J. Milne, Effect of
calcination conditions and excess alkali carbonate on the
phase formation and particle morphology of Na0.5 K0.5 NbO3
powders, J. Am. Ceram. Soc. 90 (2007) 1650–1655,
http://dx.doi.org/10.1111/j.1551-2916.2007.01629.x.
[33] K. Kakimoto, K. Akao, Y. Guo, H. Ohsato, Raman scattering
study of piezoelectric (Na0.5 K0.5 )NbO3 –LiNbO3 ceramics, Jpn.
J. Appl. Phys. 44 (2005) 7064–7067,
http://dx.doi.org/10.1143/JJAP.44.7064.
[34] N. Klein, E. Hollenstein, D. Damjanovic, H. Trodahl, N. Setter,
M. Kuball, A study of the phase diagram of (K,Na,Li)NbO3
determined by dielectric and piezoelectric measurements,
and Raman spectroscopy, J. Appl. Phys. 102 (2007) 014112,
http://dx.doi.org/10.1063/1.2752799.
[35] W.L. Zhu, J.L. Zhu, Y. Meng, M.S. Wang, B. Zhu, X.H. Zhu, J.G.
Zhu, D.Q. Xiao, G. Pezzotti, Structural characteristics of
Mg-doped (1−x)(K0.5 Na0.5 )NbO3 −xLiSbO3 lead-free ceramics
as revealed by Raman spectroscopy, J. Phys. D: Appl. Phys. 44
(2011) 505303,
http://dx.doi.org/10.1088/0022-3727/44/50/505303.
[36] D.C. Sinclair, A.R. West, Impedance and modulus
spectroscopy of semiconducting BaTiO3 showing positive
temperature coefficient of resistance, J. Appl. Phys. 66 (1989)
3850, http://dx.doi.org/10.1063/1.344049.
[37] U. Robels, G. Arlt, Domain wall clamping in ferroelectrics by
orientation of defects, J. Appl. Phys. 73 (1993) 3454,
http://dx.doi.org/10.1063/1.352948.
[38] P. Jakes, E. Erdem, R.-A. Eichel, L.D. Jin, Damjanovic, position
of defects with respect to domain walls in Fe3+ -doped
Pb[Zr0.52 Ti0.48 ]O3 piezoelectric ceramics, Appl. Phys. Lett. 98
(2011) 072907, http://dx.doi.org/10.1063/1.3555465.
[39] A. Pramanick, A.D. Prewitt, J.S. Forrester, J.L. Jones, Domains,
domain walls, and defects in perovskite ferroelectric oxides:
a review of present understanding and recent contributions,
Crit. Rev. Solid State Mater. Sci. 37 (2012) 243–275,
http://dx.doi.org/10.1080/10408436.2012.686891.
478 b o l e t í n d e l a s o c i e d a d e s p a ñ o l a d e c e r á m i c a y v i d r i o 6 2 (2 0 2 3) 468–478

[40] D.M. Marincel, H. Zhang, A. Kumar, S. Jesse, S.V. Kalinin,
W.M. Rainforth, I.M. Reaney, C.A. Randall, S.
Trolier-McKinstry, Influence of a single grain boundary on
domain wall motion in ferroelectrics, Adv. Funct. Mater. 24
(2014) 1409–1417, http://dx.doi.org/10.1002/adfm.201302457.
[41] Y.-J. Dai, X.W. Zhang, K. Pi, Morphotropic phase boundary
and electrical properties of lead-free ceramics, Chem. Appl.
Phys. Lett. 94 (2009) 042905, http://dx.doi.org/
10.1063/1.3076105.
[42] Q. Hu, H. Du, W. Feng, C. Chen, Y. Huang, Studying the roles
of Cu and Sb in K0.48 Na0.52 NbO3 lead-free piezoelectric
ceramics, J. Alloys Comp. 640 (2015) 327–334,
http://dx.doi.org/10.1016/j.jallcom.2015.03.223.