Journal of the European Ceramic Society 42 (2022) 307–326

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Journal of the European Ceramic Society

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Review article

Engineered feldspar-based ceramics: A review of their potential in

ceramic industry
V. Fuertes a, b, *, J.J. Reinosa b, J.F. Fernández b, E. Enríquez b, **
a
Centre d’optique, Photonique et Laser, 2375 Rue de la Terrasse, Université Laval, Québec, (QC), G1V 0A6, Canada
b
Dept. Electrocerámica, Instituto de Cerámica y Vidrio, CSIC, Kelsen 5, 28049, Madrid, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: Feldspars are the most abundant mineral in the earth’s crust, however, their interest in ceramic industry goes
Ceramic raw material beyond their abundancy. The unique compositional and structural features as well as the many outstanding
Synthetic feldspar properties that feldspars own, make them to be widely used as raw material for the ceramic industry. Moreover,
Engineered feldspar
multiple works have demonstrated that engineered feldspar-based ceramics are very promising for their use in
Ceramic industry
applications such as ceramic tiles, dielectrics or phosphors, among others, and therefore, in this article, a
Feldspar-based ceramic
comprehensive review on their dielectric, mechanical, optical and thermal properties is presented. This review
intends to provide an up-to-date outlook of the possibilities that engineered feldspars offer to their application in
ceramic industry, discussing future prospects and challenges that might ease the opening up of new horizons for
future applications in ceramic sector.

1. Introduction
Feldspars are anhydrous aluminosilicates that constitute the most
abundant mineralogical group of the earth’s crust, covering around 58
% of the composition of many rocks, being an essential component in
igneous, metamorphic and sedimentary rocks [1,2]. The abundance of
feldspars in nature make that they have received considerable attention
throughout history, having emerged numerous studies trying to char­
acterize their structural, physical and chemical features by different
material characterization techniques (TEM, HRTEM, Raman and IR
spectroscopy, XRD, NMR, neutron diffraction, luminescence…) in order
to extract valuable information about Earth from these elements that are
abundantly presented in nature [3–6]. However, the interest of feldspars
go beyond the basic geology or material science and owing to their
composition, feldspars are widely used as raw materials in the glass,
~60 %, and ceramic manufacture, ~35 %. Feldspar raw materials are a
source of alumina (Al2O3), alkali (Na2O and K2O), and silica as well as
they are used as fluxing agents to form a glassy phase at lower tem­
peratures [7–9]. Alkali feldspars are principally used in glassmaking and
ceramics, sodium-rich plagioclases are mostly used in ceramics while
calcium-rich plagioclases in several construction products, such as
fiberglass or to strengthen glass-reinforced plastic products [10].
However, their application is also extended to other fields: fillers and
extenders (in applications such as paints, plastics and rubber), for
biomedical applications (as dental porcelains) or as dating element in
Earth Sciences and Archaeology (K-Ar, Ar-Ar, luminescence dating etc),
among others [6,9].
Given its economic relevance, more than 40 countries extract feld­
spar significantly among the more than 70 countries in the world that
possess significant feldspar resources [10]. The annual production of
feldspars in the world stands at ~26 million metric tons (Mt), in 2019,
being the main feldspar producing countries Turkey (~7.5 Mt), Italy
(~4 Mt), India (~4 Mt) and China (~2 Mt) [10,11]. The world feldspar
market was USD 547.0 million in 2017 and it is estimated to reach USD
745.7 million by 2022, being this growth justified by the production
increase of ceramics, glasses and fillers products [12].
On the other hand, their structural richness and remarkable prop­
erties as minerals have generated abundant scientific literature devoted
to reproduce them by a wide range of synthesis methods such as hy­
drothermal route, sol-gel, cationic exchange, glass-ceramic route, etc
[13–20]). Other studies have been focused on systematic study of their
properties, whereas, recently, a step further in feldspar materials comes
with their structural and microstructural engineering in order to bestow
novel functionalities. All these works have shown that synthetic

* Corresponding author at: Centre d’optique, Photonique et Laser, 2375 Rue de la Terrasse, Université Laval, Québec, (QC), G1V 0A6, Canada.
** Corresponding author at: Dept. Electrocerámica, Instituto de Cerámica y Vidrio, CSIC, Kelsen 5, 28049, Madrid, Spain.
E-mail addresses: victor.fuertes-de-la-llave.1@ulaval.ca (V. Fuertes), esther@icv.csic.es (E. Enríquez).

https://doi.org/10.1016/j.jeurceramsoc.2021.10.017
Received 4 September 2021; Received in revised form 7 October 2021; Accepted 12 October 2021
Available online 18 October 2021
0955-2219/© 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
V. Fuertes et al.
feldspars are very promising materials for their use in several applica­
tion fields, as ceramics, such as building materials, electronic or opto­
electronic sector, among others [21–24].
In scientific literature, the features of feldspars as raw minerals are
reviewed, justifying their great use, namely, in the glass and ceramic
industry [1–3,25–27]. Nevertheless, so far, the enormous potential that
synthetic feldspars own have been not reviewed, according to the best of
authors’ knowledge. Thus, this review article intends to give an
up-to-date overview of feldspars in their application to ceramic industry
via two topical areas, as raw material and as engineered feldspar-based
materials, in further detail. For that purpose, it will be also revised main
aspects about them such as composition and structural features that
justify their wide use in the current ceramic sector and the great range of
possibilities that they offer through their engineering and the incorpo­
ration of new functionalities. Finally, some conclusive remarks, future
prospects and challenges will be discussed.
2. Mineral feldspars: structural and compositional
considerations
Feldspars are minerals that belong to the group of silicates. The
fundamental building unit of silicates is the silicon tetrahedron,
(SiO4)4− . Depending on how these tetrahedra are joined, different sub­
groups will be differentiated. Among them, it is worth mentioning the
group of tectosilicates, also known as framework silicates, which are
characterized by having a structure with rings of tetrahedra joined by
their four vertices, forming a three-dimensional framework. Within the
tectosilicates we find different groups, such as quartz, zeolites, scapo­
lites, feldspathoids and feldspars.
Feldspars are aluminosilicates whose formation occurs when in some
silicon tetrahedra there is a substitution of Si4+ by Al3+, which causes a
positive charge defect that will be compensated by different alkali and
alkaline-earth cations (Fig. 1). The framework of feldspars consists of
rings of four tetrahedra, where the corners of each one are occupied by
oxygens and links two tetrahedra. In their centres, Si4+ or Al3+ cations
are located with a Si4+/Al3+ ratio variable, depending on the feldspar
composition which also conditions the different alkali and alkaline-earth
cations that are located in the interstices between such tetrahedra. The
Si4+/Al3+ ratio is 3:1 for monovalent cations (MAlSi3O8 with M typically
K1+ or Na1+ and rarely Rb1+) and 2:2 for divalent ones (M’Al2Si2O8 with
Fig. 1. Ternary diagram for the solid solution of feldspars.
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Journal of the European Ceramic Society 42 (2022) 307–326
M’ typically Ca2+, Ba2+ or Sr2+ and rarely Zn2+ and Mg2+), as it can be
seen in Fig. 2a and b for NaAlSi3O8 and CaAl2Si2O8, respectively. In
terms of composition, feldspars are generally described in a ternary
system formed mainly by three large groups: potassium, sodium and
calcium feldspars [3,28,29]. Feldspars appear often mixed, forming
solid solutions instead of a pure phase. The range of existing composi­
tions generally gives rise to two big groups: alkali feldspars and
plagioclase, Fig. 1. The composition in the group of alkali feldspars
varies in the system K-end member (KAlSi3O8, orthoclase and micro­
cline), Na-end member (NaAlSi3O8, albite) and in the plagioclase group
in the system Ca-end member (CaAl2Si2O8, anorthite), Na-end member.
Plagioclase is commonly defined based on the content of anorthite (An)
in the solid solution. Typically, plagioclases are classified as: albite
(An0-An10), oligoclase (An10-An30), andesine (An30-An50), labra­
dorite (An50-An70), bytownite (An70-An90) and anorthite (An90
-An100), as seen in Fig. 1. In the case of the solid solution of alkali
feldspars, a possible classification in terms of composition is: K-sanidine
(80–100 % of KAlSi3O8), Sanidine (50–100 % of KAlSi3O8), Na-sanidine
(36–50 % of KAlSi3O8) and anorthoclase, (10− 36 % of KAlSi3O8) [1,6].
However, in the current literature, this mineralogical classification is
broadened and the concept of feldspar is extended to other structures in
which the charge balance is kept despite Si or Al are replaced, such as
M+AB3O8 or M’2+A2B2O8 structures where A might be Al or Ga and B
might be Si or Ge [30,31]. On the other hand, zinc feldspars are also
considered, such as CaZnSi3O8 [32], BaZnSi3O8 [33,34] and SrZnSi3O8
[35].
In addition to their chemical composition, a complete characteriza­
tion of feldspars requires to consider several additional factors such as
the symmetry of their structure (C 1, C2/m or I 1) and the order/disorder
in the distribution of Al-Si in the feldspar lattice. Order/disorder in
feldspar is explained in terms of the tetrahedral positions that Al3+
atoms occupy inside of the lattice. Feldspars can have a triclinic or a
monoclinic structure. In triclinic structures, as albite or microcline, four
symmetrically non-equivalent sites exist (Fig. 2a), designated as T1(0),
T1(m), T2(0), and T2(m) while only two exist in the monoclinic structure
(T1 and T2). In ordered structures, Al is placed in T1(0) positions
(Fig. 2a), however when temperature increases, the disordering process
starts. Al migrates from T1(0) sites to T1(m), T2(0), and T2(m) sites. In a
perfect disorder state, 25 % of Al is placed in T1(0) positions, and the
other 75 % is equally distributed between T1(m), T2(0), and T2(m) sites.
Based on that explanation, monoclinic structures cannot be fully ordered
[28].
Taking into account these structural considerations, several poly­
morphs are distinguished for each of the three end-members of feldspar
group (Table 1). Regarding end-members of plagioclase group, albite
might be found with a triclinic (space group C1) or monoclinic structure
(space group C2/m) and have different polymorphs in which Al–Si
order/disorder varies. Low albite is the most ordered specie (Fig. 2a).
Besides, albite has three different high-temperature polymorphs, high
albite, analbite and monoalbite, in which disorder increases regarding
the ordered structure (Table 1). Further details about these polymorphs
goes beyond the scope of this paper and can be found in [3,36,37]. In
contrast, anorthite is generally triclinic with space group I 1, which is
mostly ordered although a partial disordering can be attained by tem­
perature effect, above 2000 ◦ C, far greater than the melting point.
Therefore, anorthite is not as interesting as alkali feldspars for applica­
tions in which the grade of structural order/disorder is seized [28]. The
potassium end-member group is comprised, on the one hand, by
microcline, which has a triclinic structure and can be found as low
microcline (fully ordered) and intermediate microcline (partly disor­
dered) and, on the other hand, orthoclase, which is monoclinic and fully
disordered [1]. All of these features are briefly summarized in Table 1.
At high temperatures, the solid solution of alkali feldspars occurs,
distinguishing sanidine and anorthoclase, both with a monoclinic
structure and belonging to space group C2/m. Regarding order/
V. Fuertes et al. Journal of the European Ceramic Society 42 (2022) 307–326

Fig. 2. Four-membered tetrahedral ring characteristic of triclinic a) low albite and b) anorthite structure. Each tetrahedron is centred by Si (yellow atoms) or Al
(blue atoms), with a Si/Al ratio of 3:1 in a) and 2:2 in b). Tetrahedra are linked by oxygen atoms (red atoms). In a) sodium atom appears in orange, while if it is
replaced by potassium one, the triclinic structure of microcline is depicted. In anorthite, b), calcium atom is depicted in pink.

decomposition phenomena. There are different types of intergrowths

Table 1
according to the size of the domains: sub-X ray perthite (less than 15 Å),
Classification of the three end-members of feldspar group attending to their
X-ray perthite (~1 μm), cryptoperthite (1− 5 μm), microperthite (5− 100
chemical composition, Si/Al distribution, structure and space group [3,5,28].
μm) and macroperthite (100− 1000 μm) [42]. The intergrowth is
Chemical Specie Si/Al Structure Space compositionally modulated and different types of intergrowth are pre­
composition distribution group
sented in plagioclase feldspars for the following composition ranges:
Fully An1–25 (peristerite intergrowth), An46–60 (Bøggild intergrowth), and
Orthoclase Monoclinic C2/m
disordered
An67–90 (Huttenlocher intergrowth) [3,28]. Recently, this phenomenon
K-feldspars Low Microcline Fully ordered Triclinic
Intermediate Partly C1 has been also observed in a synthetic Na-rich plagioclase, as first time
Triclinic
Microcline disordered [43].
Analbite
Fully
Triclinic
Spinodal decomposition is not exclusive of feldspars and is a phe­
disordered nomenon of great structural interest from a practical point of view, since
Fully
High albite
disordered
Triclinic
C1 it is a mechanism that which microstructures can be generated that
Na-feldspars Intermediate Partly significantly improve the physical properties of the materials in ques­
Triclinic
albite disordered tion. It has been used in a wide range of materials, such as: thermo­
Low albite Fully ordered Triclinic electric materials, polymers, magnetic materials and glasses, as well as
Fully
Monoalbite Monoclinic C2/m feldspar [28,44–48].
disordered
C1
Apart from the three end-members of the feldspar solid solution
Anorthite Disordered Triclinic
Ca-feldspar Mostly
depicted in Fig. 1, BaAl2Si2O8 and SrAl2Si2O8 feldspars have attracted a
Anorthite Triclinic I1 lot of attention because of its high melting point, low thermal expansion
ordered
coefficient, high mechanical strength, chemical inertness and their
remarkable dielectric properties such as low dielectric constant and
disorder, sanidine is usually classified in high and low sanidines, which dielectric losses [49–53].
are fully and partly disordered, respectively. In the case of anorthoclase,
they are generally disordered feldspars [38]. 3. Uses of feldspars in ceramic industry
However, these three components do not have the ability to mix
completely and there is an unmixed zone, as it can be seen in Fig. 1, also 3.1. Feldspar as raw materials
known as miscibility gap that appears for the compositions between
anorthite and potassium feldspars. In this range of compositions there Feldspars have been used in ceramic industry as flux element
will be no solid solution, but crystals with a composition rich in potas­ (Fig. 3a), to obtain a wide range of ceramics such as stoneware materials
sium on the one hand, and rich in calcium on the other hand. Such [54,55], ceramic wares [56], porcelains [57,58], porcelain stoneware
unmixed zone will depend drastically on the physical and chemical [59], bricks [60] and glass-ceramics [61,62]. The role of alkali feldspar,
conditions of the feldspars involved, being very sensitive to changes in mainly Na and K cations, is to decrease the melting temperature of the
temperature, composition and pressure [3]. glass batch and favors the melting of other minerals that are presented in
According to the free energy diagram of the involved solid solution, the formulation. On the other hand, the contribution of feldspars with
if a solid solution is cooled below the "solvus" temperature, which de­ Al3+ and Ca2+ cations increase both physical and chemical resistance of
fines its solid solubility limit, a phase separation occurs [22]. This pro­ the product [10].
cess is also known as an exsolution or unmixed process and it is Feldspars can be extracted principally from naturally-occurring
energetically more favourable than a solid solution. This process of quarries: granite pegmatite, which is the traditional source of feld­
exsolution can occur through a phenomenon called spinodal decompo­ spars, granitroids, aplites, acid volcanics and subvolcanics, nepheline
sition or by nucleation and growth [39–41]. Spinodal decomposition is a syenites and phonolites, feldspathic arenites, metamorphics, albitites or
mechanism at atomic level that leads to a coherent growth of the epithermal alterations [26,27]. An exhaustive description of these
involved phases. On the other hand, if the end-members of the solid feldspar sources goes beyond the scope of the present paper and the
solution have remarkably different structures, the exsolution is pro­ reader is addressed to other works about flux deposits [25–27]. Their use
duced by nucleation and growth [40]. improves the performance of the final ceramic product, such as dura­
At low temperatures, typically below 600 ◦ C, although it depends on bility, whiteness, strength, toughness, fade, chemical resistance and
the potassium and sodium content, alkali feldspars show spinodal cements the crystalline phases of other ingredients, softening, melting
and wetting other batch constituents [8]. All of these properties make

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Fig. 3. a) Amount of feldspar as flux agent (wt. %) used in industrial compositions for main ceramic products. No variable is depicted in y-axis. b) Ratio between
feldspar production and its demand in ceramic tile industry: global output from1990 to 2016. Adapted from [27].

feldspars being used in many applications of our daily life, in which the price quotations might be only considered as a guide price. For instance,
feldspar content vary, such as dinnerware (17–20 %), sanitary wares, the cost for U.S. ceramic-grade feldspar per metric ton, in 2003, was in
floor tiles (55− 60 % of feldspar content), wall tile (0–11 %), the range of USD 66–83 for sodium feldspar and around USD 138 for
high-tension electrical porcelains (25–35 %), dental porcelains (60− 80 potassium feldspar. These prices does not include insurance or transport
%), kitchen and ovenware (10 %), (Fig. 3a), enamels, frits, tablewares, costs [9].
countertops, refractories, etc [9]. In the manufacture of traditional ce­
ramics, feldspars can be considered as one of the main ‘’backbones of the
3.2. Synthetic feldspar-based materials
ceramic and porcelain industry’’, being the second most large ingredient
after clay [2].
3.2.1. Synthesis and production process
One of the most important aspects to take into account about the use
The great industrial impact mentioned above makes the study of
of feldspars in the ceramic industry is their granulometry, which must be
feldspars interesting, both from a fundamental science point of view and
smaller than 74 μm since its fluxing power is inversely proportional to its
for the possible exploration of their properties for being used in new
grain size [8]. Another important factor is their purity, which is highly
applications. For all these reasons, there is a growing interest to study
determined by the type of final product. One of the most detrimental
the artificially synthetize of feldspars to diversify its field of application.
impurities is iron since when the amount of contaminant is larger than
In ceramic industry, feldspars crystallization usually appear as a sec­
0.5 %, it provides a dark colouring as well as other irregularities to the
ondary phase after the sintering, which can be very varied such as po­
final ceramic product and, therefore, worsens its quality. For example, in
tassium feldspars [59,64], albite [59], anorthite [65,66], plagioclases
the case of the white dishes, the maximum allowed iron amount is 0.1 %
[67,68], or barium feldspar [69], among others. However, the crystal­
whereas when brightness is not concerning, 2–3 % of Fe2O3 can be
lization behaviour of feldspars as an isolated phase is also widely dis­
presented in the composition [8,26].
cussed in literature, partly on account of its complexity. Crystal growth
One of the main applications of feldspars is ceramic tiles (wall tile,
rate strongly depends on the fusion entropy of the involved material that
floor tile, vitrified tile and industrial tile), which simultaneously is one of
for the ternary system is 72.2, 46.3 and 36.0 J/Kmol, respectively for
the most demanded in the ceramic market, with a production of around
anorthite, albite and orthoclase. Consequently, alkali feldspars are much
13.1 billion m2 in 2016. The global ceramic tiles market has being
more difficult to crystallize that alkaline-earth feldspars [29]. Despite of
valued around US$ 70.9 billion in 2018 and represents a Compound
that, most of feldspars might be obtained by several synthesis methods
Annual Growth Rate (CAGR) of 9.1 % during 2011− 2018. This market is
such as hydrothermal method, cation exchange, solid-state method,
expected to reach US$ 107.2 billion by 2024, exhibiting a CAGR of 7.2 %
crystallization of glasses or the corresponding glass-ceramic by devitri­
during 2019–2024 [63]. This is partly accounted for the expecting in­
fication. Other synthesis routes, less common for the synthesis of syn­
crease in construction remodeling market, principally in growing
thetic feldspars, as sol-gel, Pechini, electrofusion, combustion,
economies such as China, Japan or India. In last years, there is an up­
mechanochemical activation, coprecipitation or cellulose assisted liquid
ward trend of using ceramic tiles, instead of marble, wood or other
phase precursor (LPP), among others, have also been implemented, as it
traditional flooring materials because of their highest durability and
is discussed below and described in Table 2.
their frost and thermal shock resistance [10]. Moreover, the recent boom
Solid-state method has been widely considered in literature to obtain
of ceramic tile inkjet technology which allows copying or producing all
feldspar-based materials for several fields of application, especially for
types of realistic designs on ceramic tiles at affordable costs may boost
industry uses due to its low complexity, low cost and reduced pollution,
this continuous growth of the ceramic tile market (Fig. 3b), being one of
among others. The reagents employed are typically oxides and carbon­
the main driven forces for the possible increase in the demand of feld­
ates and the main pursued phases are alkaline-earth ones, such as Ca-,
spars in next years.
Sr- and Ba- feldspars [49,53,70–72]. Although in some other occasions,
The annual production of feldspars in the world is estimated to be
other different raw materials are also used, for instance kaolin or coal fly
around 26 Mt in 2019. The feldspar production is led by Turkey (~7.5
ash, as in the case of celsian and Sr-celsian felspars [52,73–78]. This is
Mt) and followed by Italy (~4 Mt), India (~4 Mt) and China (~2 Mt)
also illustrated in the synthesis of anorthite porcelains, in which very
[10,11]. The world feldspar market was USD 547.0 million in 2017 and
varied sources of calcium oxide have been considered in literature (such
it is estimated to attain USD 745.7 million by 2022. This considerable
as of wollastonite, aluminous cement, calcite, colemanite, limestone, or
growth is justified partly by the production increase of ceramics [12].
dolomite, among others) and as a source of silica or alumina such as
Prices for feldspars are dependent on several factors such as application,
kaolin, kaolinite, ball clay, quartz, or the own feldspars, as it is discussed
particle size, quality, quantity, source, and type of material [9]. Thus,
in Section 3.1 [79–84].

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Table 2
Summarize of main synthesis methods considered in literature for different alkali and alkaline-earth feldspars.
Synthesis Feldspar compositions
method
Na- K- Ca-feldspar Ba-feldspar Sr-feldspar Mg-feldspar Zn- Plagioclase
feldspar feldspar feldspar

Solid-state [85,86] [31,87, [50,70,71,72,79,80,81, [30,49,52,72,74,75, [49,52,53,73,93,101,102, [122,123,124, [33,34, [131,132]

88] 82,83,84,89,90,91,92, 76,77,78,101,102, 108,109,110,111,112,113, 125,126,127, 35]
93,94,95,96,97,98,99, 103,104,105,106, 114,115,116,117,118,119, 128,129,130]
100,101] 107] 120,121]
Hydrothermal [133, [134] [135] [136,137,138,139] [136,140] [32]
134]
Sol-gel [141, [143] [13,144,145,146,147, [150,151,152,153, [151,156] [143]
142,143] 148,149] 154,155]
Pechini [157] [157,158] [157,158,159,160]
Coprecipitation [161,162,163,164]
Cation exchange [165, [165, [168] [168] [51,169]
166] 166,167]
Combustion [170,171]
Electrofusion [172]
Mechanical [173]
activation

In other works, soft chemistry is used to overcome the disadvantages
of the solid-state method. Having a liquid phase during the synthesis
favors a larger homogeneity in the system and, consequently, ease the
targeted phase formation. Moreover, the reactions conditions allow
selecting the final particle size, being a very effective method for a
uniform incorporation of dopants in the feldspar structure. Methods
such as sol-gel allow achieving a uniform composition, high purity, and
lower synthesis temperature than other methods. For instance, Flehmig
synthetized potassium feldspars, albites and plagioclases (oligoclase and
andesine) at temperatures as low as 0− 80 ◦ C from gels of their precursor
hydroxides in aqueous solutions [143]. Kim et al. used the LPP method
to synthetize CaAl2Si2O8:Eu phosphors [174]. This method allows
making small particles, which consequently decreases sintering time and
temperature regarding the conventional solid-state reaction method.
Pechini method has also been considered since it can overcome some of
the difficulties and disadvantages commonly linked to the solid-state
method (such as long times of calcination or multiple sintering at high
temperatures) or the sol–gel process (during condensation and hydro­
lysis some segregation might occur, less homogeneity of cation distri­
bution etc). This approach has been used to synthetize alkaline-earth
feldspars phosphors, MAl2Si2O8:Eu (M = Ca, Sr, Ba) [157–160]. The
hydrothermal route has been also used to synthetize other less common
feldspars such as Rb [175,176] and Cs-feldspars [175], ammonium
feldspar [177], borosilicate feldspars [18,178].The main drawback of
these methods is the difficult scalability for industrial applications.
On the other hand, the nucleation of a stable phase from an amor­
phous one has also been extensively pursued. The large influence of the
differences on the structure between them and the number of bonds that
have to be broken strongly determine its achievement [29]. Schairer and
Bowen discussed the great difficulty associated with the nucleation and
growth of alkali feldspars from an anhydrous melt since, as Taylor and
Brown found [179], albite and sanidine glasses have 6-rings while the
corresponding crystal 4-rings, which implies the break of two
tetrahedral-oxygen bonds. Therefore, the crystal growth rate in alkali
feldspars is much lower than in alkaline earth feldspars, for each given
temperature. In plagioclases, the growth rate decreases as anorthite
content increases, being the maximum measured growth rate 2⋅10− 4
m⋅s− 1 in CaAl2Si2O8 and 3-7⋅10− 11 m⋅s− 1 in NaAlSi3O8 [180–182]. In
the alkali series, Fenn reported values of growth rate for hydrous melts,
which are in the range 2–7⋅10− 8 m⋅s− 1 for Or10Ab90 to Or50Ab50 with 2.7
wt. % of H2O, respectively [183]. For these reasons, alkali phases are
typically eluded in glass-ceramics while the obtaining of alkaline-earth
is much easier and thus it is one of the major crystalline phases of
glass-ceramics [15,19,184].
Feldspar glasses have been prepared by the typical melting-
quenching method (in which the precursors in powder form are
initially mixed, subjected to thermal treatments above their melting
temperature and finally quenched to obtain the pursued glassy struc­
ture) such as albite or anorthite glasses, also named as frits [14,
185–187], as well as glasses in the systems BaO-Al2O3-SiO2, SrO-A­
l2O3-SiO2, and CaO-Al2O3-SiO2 [188,189]. Hydrous albite glass has also
obtained by this method, since water makes easier its nucleation,
favouring the hydrolyzation of tetrahedral-oxygen bonds [141,190].
One of the most common methods for feldspar synthesis is the
crystallization from the corresponding melt of a precursor glass,
obtaining which is known as glass-ceramic. Bahat subjected the parent
glasses of the systems BaO-Al2O3-SiO2, SrO-Al2O3-SiO2, and CaO- Al2O3-
SiO2 to heat treatments at 1000 ◦ C–1100 ◦ C for times between 1 h and
several days, obtaining the correspondent glass-ceramics [188]. Since
the complexity to crystallize alkali glasses, it has been studied the effect
of different factors in their crystallization. Due to the presence of water
vapor under pressure, Bowen and Tuttle crystallized different soda and
potassium feldspars of the solid solution from their glasses [191] and
Mackenzie synthetized albite crystals from an albite glass at tempera­
tures between 450 ◦ C and 1000 ◦ C [192]. Liu et al. synthetized albite
glass-ceramics from an albite glass by devitrification, thanks to the use
of anorthite and isostructural seeding [13,14]. They also showed that
isostructural seeding is also effective to crystallize K-feldspars from their
glasses while they proved that seeds have hardly effect in the crystalli­
zation of Ca-, Sr-feldspars glasses neither in Rb- and Cs-feldspars glasses,
which could not be crystallized [193]. Barbieri et al. prepared high
densified celsian and strontium-celsian glass-ceramics [194], Li et al.
crystallized monocelsian SrAl2SI2O8 glass-ceramics by a two-step sin­
tering method [189], while Bansal et al. studied the crystallization
properties of Sr-Ba feldspars glass-ceramics by sintering them at tem­
peratures of 800–1500 ◦ C for 10 h or 20 h [195]. Bahat synthetized
SrAI2Si2O8 and CaAI2Si2O8 feldspar glass-ceramics subjecting the parent
glass (obtained by using vanadium oxide and molybdenum oxide as
nucleating agents, respectively) to thermal treatments at 1000 ◦ C for 1 h
[196], and Ohgaki synthetized glass-ceramics in the system CaO-A­
l2O3-SiO2 [187]. The processing route is even more complicated when
trying to synthesize a glass-ceramic material with high crystallinity and,
therefore, a small amount of residual vitreous phase, which usually re­
quires the use of long-term thermal treatments [197] and in some cases
the use of vacuum systems [198]. In 2008, Bernardo et al. obtained a
glass-ceramic with an estimated crystallinity of about 80 vol%, based on
crystallization of potassium feldspars (microcline and orthoclase) [17].
It was sintered at low temperature, 750 ◦ C with a heating rate of 10
◦
C/min for 2 h. Recently, in 2019 Enriquez et al. obtained
micro-nanostructured feldspar-based glass-ceramics with higher

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crystallinity, > 90 %, based on anorthite [23] and Na-rich plagioclase
crystallizations [20] by means of a fast sintering process at 1220 ◦ C for 6
min, with a heating rate of 30 ◦ C/min. This research group has recently
introduced the concept of microstructural design in feldspar-based
glass-ceramics, demonstrating that they are suitable matrices for a
microstructural engineering that allows the functionalization of the
designed glass-ceramic.
3.2.2. Functional characterization
Apart from their synthesis, the properties of feldspar crystals give rise
to a growing interest in functional applications. Initially, these studies
were very systematic and mainly based on the analysis of mechanical,
electrical or optical features to contrast them with the corresponding
ones in the natural counterparts. As ceramic market started to grow,
principally the sector of ceramic tiles, specific mechanical and thermal
properties were started to be analyzed to ensure that the products met
the demands of the market. In recent years, the advance characterization
of the feldspars diversifies its field of application paying attention to as
electronic or optic applications. For these reasons, in this section, elec­
trical, mechanical, thermal and optical properties are reviewed.
3.2.2.1. Electrical properties. Electrical properties of feldspar minerals
have been deeply discussed in literature over the years, principally their
electrical conductivity [199–202]. Since one of the main application of
ceramics is as dielectric insulator used in many microelectronic devices,
the electrical properties of synthetic feldspars-based materials were
studied at low frequency (Table 3) and in the microwave range (Table 3)
[203]. The feldspar-based ceramics were studied for low-temperature
cofired-ceramic (LTCC) technology in microwave applications, which
have to meet some requirements such as low sintering temperature,
below 1000 ◦ C, low temperature-stable dielectric constant (εr), in the
range 5− 10, to enable high speed signal transmission and low dielectric
losses (tanδ) to improve the frequency selectivity, which is translated
into high quality factors (Q × f) calculated by the expression 1/tanδ × f
[204].
In the sixties [76] it was stablished that dielectric constant and los­
ses, in hydrothermally synthetized sanidine and celsian feldspars, in­
crease quickly with decreasing frequency as temperature increases and
the most likely source of losses in these materials was cation migration
through non-perfect regions of the crystals [136]. Moreover, the
dielectric constant and dielectric losses of glasses and glass-ceramics are
approximately constant with frequency for all in the systems BaO-A­
l2O3-SiO2, SrO- Al2O3-SiO2, and CaO- Al2O3-SiO2 at 100 Hz and 10 kHz
and at different temperatures up to ~500 ◦ C [188]. The slightly larger
dielectric constant values exhibits by BaAl2Si2O8 (Table 3) than SrAl2
Si2O8 and CaAl2Si2O8 might be explained by the larger polarizability of
Ba2+ with respect to Sr2+ and Ca2+ [205]. Volume resistivity was also
evaluated and it resulted to be ~1014 Ω/cm ◦ C at about 300 ◦ C for all
feldspar stoichiometries [188]. In 2000, McCauley [49] evaluated the
dielectric properties of the Ba1-xSrxAl2Si2O8 (with x from 0 to 1) solid
solution sintered at 1500 ◦ C in the temperature range from -175 ◦ C to
200 ◦ C and at 1 kHz, 10 kHz and 100 kHz. Dielectric constants were in
the range 7–8 while dissipation factor ~10− 2-10-3. Moreover, it was
observed that the incorporation of small quantities of Sr regarding the
pure barium phase slightly diminish εr, even below that the corre­
sponding pure Sr phase while enhances the formation of the monoclinic
phase and decreases the duration of heat treatment from 72 h to 24 h
[49]. Kobayashi and Inagaki reported low values of εr = 5.3 and tan δ =
5⋅10-5 at 1 MHz for a Sr-hexacelsian ceramic obtained via solid-state
reaction and sintered at 1100 ◦ C for 1 h [73]. Krzmanc et al. studied
dielectric properties of plagioclases ceramics synthetized by solid-state
method, NaxCa1-xAl2-xSi2+xO8, sintered by fast and slow cooling. At 1
MHz, fast-cooled ceramics present εr = 5.1− 9.3 while slow-cooled ce­
ramics present εr = 5.4–8.9, increasing as anorthite content increases
[132]. In 2007, this research team investigated the KxBa1− xGa2− x
Ge2+xO8 solid solution of ceramics sintered at 970− 1100 ◦ C and study
the phase transition P21/a⇔C2/m, which showed an εr in the range
5.8− 7.1 at 1 MHz [87]. The substitution of Ba with Sr or Ca in BaAl2
Si2O8 ceramics was also studied. In both compositions, SrxBa1− xAl2Si2O8
(0≤x≤1) and CayBa1− yAl2Si2O8 (0 ≤ y ≤ 0.05), εr was ~7.3 and tanδ <
10-4 at 1 MHz and therefore, it was established that there is no signifi­
cant effect in dielectric properties despite Ca2+, Sr2+ and Ba2+ have
different dielectric polarizability [101]. Furthermore, they studied the
dielectric behavior of Sr0.05Ba0.95Al2Si2O8 ceramic and the BaM2M′ 2O8
(M = Al, Ga; M′ = Si, Ge) family sintered between 1100− 1500 ◦ C for
generally 12 h [30]. Kumar et al. prepared a crystallizable
anorthite-based glass for LTCC applications with remarkable dielectric
properties and stable over the evaluated frequency range [206]. The
addition of 30 vol% of cordierite to glass composition leads to crystal­
lization of anorthite crystalline phase after sinterization at 850− 950 ◦ C

Table 3
Comparative values of dielectric constant (εr) and dielectric losses (tanδ) at low frequencies for synthetic feldspar-based materials at room temperature. In the solid
solutions that appear in the table, x takes values 0 ≤ x ≤ 1, except for the cases in which a different range is indicated. Following abbreviations are used: Ref. =
Reference; G = glass; GC = glass-ceramic and C = ceramic.
Composition State εr tanδ Frequency Ref.
− 3
G 9.4 1.4⋅10
Hexacelsian 5 10 kHz [188]
GC 6.9− 9.3 (9.0− 800.0)⋅10−
G 8.4 1.8⋅10− 3
10 kHz [188]
Hexagonal Sr-feldspar GC 7.5− 7.8 8.0− 9.7⋅10− 3
C 5.3 0.5⋅10− 4 1 MHz [73]
G 7.1 1.6⋅10− 3
Hexagonal Ca-feldspar + traces of An 10 kHz [188]
GC 7.4 2.1⋅10− 3
4
C 7.4− 7.8 (3.0− 223.0)⋅10− 10 kHz [49]
Ba1-xSrxAl2Si2O8
C 7.0 (x = 0.05) – 1 MHz [30]
NaxCa1-xAl2-xSi2+xO8 C 5.1− 9.3 – 1 MHz [132]
KxBa1− xGa2− xGe2+xO8 C 5.8− 7.1 – 1 MHz [87]
SrxBa1− xAl2Si2O8 C 7.3 10− 4 1 MHz [101]
CaxBa1− xAl2Si2O8 (0 ≤ x ≤ 0.05) C 7.3 10− 4 1 MHz [101]
BaAl2Ge2O8 C 7.2 – 1 MHz [30]
BaGa2Si2O8 C 7.6 – 1 MHz [30]
BaGa2Ge2O8 C 6.8 – 1 MHz [30]
G 7.9 7.0⋅10− 4
[206]
Anorthite-based GC 6.0 3.0⋅10− 4 1 MHz
C 5.8 1.310− 3 [71]
•

Monoclinic Sr-feldspar GC 7.4− 8.4 – 1 MHz [207]

BaAl2-2x(ZnSi)xSi2O8 C 6.6− 7.3 – 1 MHz [34]
Na-rich plagioclase GC 4.6 2.2⋅10− 3 1 MHz [24]

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for 30 min, as well as cordierite, decreasing εr from 7.4–6 and tan δ to
~3⋅10-4 at 1 MHz. In 2014, Qing et al. obtained anorthite-based ce­
ramics prepared by solid-state reaction and sintered at 900 ◦ C, with low
εr, 5.8, and low tanδ = 1.3∙10-3, at 1 MHz, fulfilling the requirements for
low temperature co-fired ceramic applications (LTTC) [71]. In 2018,
El-Kheshen et al. synthetized monoclinic Sr-feldspar phase via the
solid-state reaction of nominal Sr-cordierite and borosilicate glass at
temperatures of 1200− 1350 ◦ C for 1 h with dielectric constants in the
range 7.4− 8.4 at 1 MHz [207]. Song and coworkers measured the
dependence of εr, at 1 MHZ, with temperature in zinc feldspar-based
ceramics, in the systems BaAl2− 2x(ZnSi)xSi2O8 with x = 0.2–1.0, sin­
tered at 980 ◦ C – 1250 ◦ C for 3 h [34]. Dielectric constant increases as
temperature increases and reaches the lowest value in BaZnSi3O8
ceramic, εr = 6.6, at room temperature. Fuertes et al. measured dielec­
tric properties of a Na-rich plagioclase-based glass-ceramic from room
temperature up to 800 ◦ C and 1 MHz. At room temperature they
observed that εr and tanδ are quite stable with frequency, measuring
values as low as εr = 4.6 and tanδ = 2.2⋅10-3 at 1 MHz. As temperature
increases, both parameters increase since the electrical conductivity of
the system is thermally activated and based on hopping processes of
alkaline elements, being more pronounced at low frequencies [24].
According to values tabulated in Table 3, the lowest εr is reached in this
micro-nanostructured Na-rich plagioclase-based glass-ceramic, while
keeping low dielectric losses. The authors synthetized this
glass-ceramics by a fast-sintering route at 1220 ◦ C for 6 min with very
high crystallinity, >94 vol.%, which is a key parameter to take into
consideration since in this kind of system, glassy phase provides a free
path to these mobile ions alkali and alkaline-earth ions to move,
increasing the conductivity of the system.
The works discussed above evince that dielectric properties of feld­
spars are dependent on composition, cooling rate and sintering tem­
perature, which is interesting for potential applications, since the adjust
of their dielectric constant and dielectric losses is possible by the opti­
mization of those factors. Most of the works previously discussed, do not
take into account the crystalline phase content reached in the synthetic
feldspar-based material despite its direct influence in its dielectric
properties since glassy phase increases dielectric losses, complicating
partly their comparison. Therefore, future works on this line should
consider it and carry out more in-depth studies to improve the current
state-of-the-art and allow the comparison of the same compositions
between different works.
In recent years, there have been several works focused on feldspar-
based microwave dielectric ceramics (see Table 4), based on plagio­
clase feldspar-type and alkali-feldspar-type structures. These
compounds typically have chemical formulas such as A[B2C2]O8
(A–– Ca, Sr, Ba; B–– Al, Ga; C–– Si, Ge) and A[BC3]O8 (A– – K, Na; B–– Al,
Ga; C– – Si, Ge). Krzmanc et al. dielectrically characterized different
feldspars-based ceramics synthetized by solid-state reaction techniques
[30,31,87,101,131,132]. Albite and anorthite feldspar-based ceramics
were synthetized and sintered in the range 1000− 1070 ◦ C and
1300− 1500 ◦ C, respectively. They observed that a slow cooling (0.5
◦
C/min) during sintering improved dielectric properties regarding fast
cooling. [131]. A wide range of sodium and calcium plagioclases were
also studied, obtaining the best quality factors, Q x f = 17,600 GHz, in
sodium plagioclases with a composition of Na0.8Ca0.2Al1.2Si2.8O8, sin­
tered at 1100 ◦ C [132]. In these works, it was observed that τf
approached to zero in Na-rich compositions while is significantly higher
in Ca-rich ones. Moreover, they studied the influence in dielectric
properties of substitutions of Ba with Sr or Ca in BaAl2Si2O8 ceramics
sintered at 1500 ◦ C. In CayBa1− yAl2Si2O8 (0 ≤ y ≤ 0.05) ceramics Q × f
values markedly decrease with substitution, reaching values Q × f ~28,
000–61,000. In the case of SrxBa1− xAl2Si2O8 (0≤x≤1), it is observed a
linear decrease of Q × f values up to x = 0.4, followed by an increase for
x = 0.5 and a decrease again for 0.5≤x≤1. The maximum Q × f values
are up to 77,700 GHz which are obtained by sintering for 40 h, while a
reduction of sintering time to 12 h leads to a decrease of Q × f values to
70,600 GHz, which can be associated with a decrease of Al:Si ordering.
For both compositions, ε = 7.2 at 10.5 GHz and remains independent of
the substitutions, whereas τf decreases in SrxBa1− xAl2Si2O8 from -22
ppm/◦ C (x = 0) to -30 ppm/◦ C (x = 1) [101]. Based on these results, this
research team optimized the Sr0.05Ba0.95Al2Si2O8 composition, by sin­
tering at 1400 ◦ C for 162 h [30]. Furthermore, the family BaM2M′ 2O8 (M
= Al, Ga; M′ = Si, Ge) sintered at 1100− 1450 ◦ C for 12 h was investi­
gated. At 12 GHz, all the compounds exhibit an εr 7–8 and a τf of that
ranges from − 26 to -32 ppm/◦ C. Regarding Q × f values, the highest
ones and the best reported one in literature, are obtained in BaGa2Ge2O8
ceramic, with Q × f values 106,400 GHz [30]. Ge-O bonds are weaker
than Si-O bonds which increases the tetrahedral ordering kinetics of
Ge-containing feldspars and consequently make that sintering temper­
ature and time are considerably reduced. This formulation seems to be
even more promising for microwave applications and LTCC technology
than traditional MAl2Si2O8 feldspars (M = Ca, Sr, Ba). In 2018 Yao et al.
studied the effect of the addition of ZBAS glass (ZnO-Al2O3-SiO2-B2O3)
into the barium feldspar system BaAl2Si2O8 obtaining Q × f of 28,058
GHz, εr = 6.7 and τf=–29.79 × 10–6 ◦ C–1 for a 3% of ZBAS addition and a
sintering temperature of 1360 ◦ C [208]. Moreover, the addition of
Li2O-B2O3-SiO2 (LBS) glass was also studied, reaching the best results for
0.3 wt. % of addition, Q x f values of 34,570 GHz, εr = 6.7 and τf =–15.97

Table 4
Comparative values of dielectric constant (εr), Q x f and τf at microwave frequencies for feldspar-based ceramics. The considered temperature range for τf analysis is
also indicated. Following abbreviations are used: Freq. = frequency; Ref. = Reference.
εr Q×f Freq. (GHz) τf τf Tª range Ref.
(ppm/◦ C) (◦ C)

NaAlSi3O8 – 11,200 – − 5
20− 60 [131]
CaAl2Si2O8 – 11,000 – − 130
NaxCa1-xAl2-xSi2+xO8 4.0− 8.0 4,400− 17,600 10.5 (− 130) - (− 5) 20− 60 [132]
KxBa1− xGa2− xGe2+xO8 5.9− 7.0 12,680− 106,400 12 (− 27) - (− 21) 20− 60 [87]
SrxBa1− xAl2Si2O8 7.2 ~35,000− 77,700 10.5 (− 30) - (− 22) 20− 60 [101]
Sr0.05Ba0.95Al2Si2O8 7.1 92,600 12 − 22 20− 60 [30]
CaxBa1− xAl2Si2O8
7.2 ~28,000− 61,000 10.5 – 20− 60 [101]
(0 ≤ x ≤ 0.05)
CaxBa1− xAl2Si2O8
6.1− 7.2 12882− 24335 8 (− 119) - (19) 25− 85 [72]
(0≤x≤0.75)
BaAl2Ge2O8 7.5 74,100 − 32
BaGa2Si2O8 7.6 62,300 12 − 32 20− 60 [30]
BaGa2Ge2O8 6.9 106,400 − 26
Ba1-xMgxAl2Si2O8 5.6− 6.4 11,046− 16,943 12 (− 52) - (− 31) 25− 85 [210]
BaAl2Si2O8-ZBAS 6.1− 6.9 13,110− 28,058 12 (− 52) - (− 26) 25− 85 [208]
BaAl2Si2O8-LBS 6.1− 6.7 13110− 34570 12.5 (− 52)- (− 16) 25− 85 [209]
BaAl2− 2x(ZnSi)xSi2O8 6.5− 7.3 ~5,000− 52,401 15 (− 63) - (− 22) 30− 80 [34]
Ba1-xSrxZnSi3O8 6.1− 6.6 28,986− 78,064 12− 14 (− 33) - (− 24) 30− 80 [35]

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× 10–6 /℃, lowering sintering temperature, for any addition of LBS,
from 1400 ◦ C to 1275 ◦ C [209]. Xiaojing studied the Ba1-xCaxAl2Si2O8
(0≤x≤0.75) solid solution and determined that Ca favours the trans­
formation from hexacelsian to celsian, which is complete for x≥0.05.
The best results were obtained for x = 0.05 [72]. Recently, in 2018 and
2019, Song and coworkers have studied the microwave properties of a
new family with feldspar structure, zinc feldspar-based ceramics, in the
systems BaAl2− 2x(ZnSi)xSi2O8 and Ba1-xSrxZnSi3O8 with x = 0.2–1.0 [34,
35]. The best dielectric properties are exhibited for x = 1, in the two new
kinds of plagioclases developed, BaZnSi3O8 sintered at 1100 ◦ C and
SrZnSi3O8 at 1150 ◦ C.
Generally, the best dielectric behaviors at high frequency are ach­
ieved for ceramics that require very long thermal treatments, 12− 162 h,
to obtain a good densification. Future works in this field should be
focused on optimizing green body preparation and sintering processes in
order to develop high-performance ceramics that take into consideration
the energy saving in ceramic industry.
The study of the mechanism of electrical conductivity (σ) in synthetic
feldspars, both in AC and DC, has also been considered in literature. The
electrical conductivity of synthetic alkali feldspars and anorthite was
studied by means of impedance spectroscopy at 673− 1173 K and
ambient pressure (P), following an Arrhenius law and it was established
that more opened structures are more conductive than closed ones
(σAlbite > σmicrocline > σAnorthite) [211]. Glasses have also been considered
in literature. The pressure dependence, in the range 0.3− 6 GPa, of the
glass transition temperature (Tg) of anorthite and albite glasses affect the
activation energy of their electric conductivity. It was observed that
activation energy below Tg is less than above Tg for P<1 GPa, and almost
independent for higher pressures. It was established two classes in terms
of the correlation of dielectric relaxation under pressure: glasses with
strongly (as anorthite, in which the activation energy of the dielectric
relaxation rises with P) and weakly coupled viscous and dielectric re­
laxations (as albite, in which activation energy decreases with P) [212].
Moreover, in albite glasses, it was observed that electrical conductivity
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Journal of the European Ceramic Society 42 (2022) 307–326
was based on Na transport, increasing with temperature and water
content but decreasing with pressure (Fig. 4a) [186].
Afterwards, in 2015, Hu et al. [213] analyzed the behavior of
anorthite synthetized by solid-state method at 873–1173 K and pres­
sures of 1.0–3.0 GPa (Fig. 4b). They observed a rise of electrical con­
ductivity with increasing temperature and a slightly decrease with the
rise of pressure (at constant temperature), obtaining activation en­
thalpies of 1.86− 1.91 eV for 1.0–3.0 GPa, respectively. It was proposed
that the dominant charge transport mechanism was the hopping of Ca2+
from aluminum positions to near oxygen positions. Conductivity values
reported by Bagdassarov et al. [212] in anorthite glass at 3 GPa were
more than half order of magnitude larger than in anorthite crystalline
(Fig. 4b), while activation enthalpies were much lower (1.17 eV at 3.0
GPa and 1.22 eV at 4.5 GPa). These observed differences might be
explained by the stronger linkages of calcium ions in the crystalline
network than in the glassy structure. Comparison with the synthetic
anorthite reported by Mauri [211] is complicated due to the lack of
details about experimental process, as stated Hu et al. [213]. Therefore,
in general, there is a need of further experimental details in the works
reported in literature, as it was previously mentioned for dielectric
properties of feldspars at low frequency, since structure and micro­
structure play a fundamental role in electric properties of
feldspars-based glasses and ceramics, as well as, for being able of
reproducing the existing matrices in future works.
In 2018, Fuertes et al. studied the electrical conduction of a novel
fast-sintered micro-nanostructured Na-rich plagioclase-based glass-
ceramic, heating up to 800 ◦ C. By impedance analysis (Nyquist plot),
the behavior of nanocrystals contribution was distinguished, which are
the most resistive contribution, from microcrystals contribution. The
material has a negative temperature coefficient of resistance (NTCR).
Moreover, DC and AC electrical conductivity measurements showed the
good insulator behavior of the synthetic feldspar, with σDC values of
7⋅10− 7–8⋅10-4 S m-1 in the temperature range considered [24]. Alter­
natively, Fuertes et al. also carried out a thorough characterization of its
Fig. 4. Electrical conductivity at different
pressures as a function of reciprocal tempera­
ture for: a) albite glass, considering different
water contents. Figure adapted from [186]. b)
Anorthite crystals (solid lines) at 1.0 GPa
(black) and 3.0 GPa (red) [213]; anorthite glass
(dotted line) at 3.0 GPa (blue) and 4.5 GPa
(pink) [212]; and synthetic anorthite at
ambient pressure (green dashed line) [211].
Figure adapted from [213]. c) Dielectric
breakdown mechanism diagram depicted on a
SEM micrograph for an albite-based glass-­
ceramic. Cation diffusion, stress (indicated by
white arrows) and temperature gradient (ac­
cording to the temperature scale) are shown.
Adapted from [214]. (For interpretation of the
references to colour in this figure legend, the
reader is referred to the web version of this
article).
V. Fuertes et al. Journal of the European Ceramic Society 42 (2022) 307–326

dielectric strength in DC domain. They observed that the combination of
a hierarchical micro-nanostructure along with high crystallinity, >94 %
Vol.%, leaded to the largest dielectric strength reported for a ceramic
insulator, > 60 kV/mm [24]. In 2019, they deepened the study of
dielectric strength for this novel engineered feldspar and carried out
measurements with temperature [214] showing that glass-ceramics
withstand temperatures up to 200 ◦ C with dielectric strengths of 44
kV/mm and 30 kV/mm for the designed Na-rich and Ca-rich feld­
spar-based glass-ceramic, respectively. Moreover, by SEM and confocal
Raman microscopy they established a dielectric breakdown mechanism
(Fig. 4c), as first time for a glass-ceramic insulator, which can be sum­
marized as follows: temperature increases sharply in the material during
the breakdown phenomenon because of the Joule effect, reaching tem­
peratures above the melting point of the residual glass presented in the
insulator that favour the drag of cations with high mobility in feldspar
compositions, such as Na+, K+ and Ca2+. The presence of several phases
and crystals with different morphology, size and composition in the
glass-ceramic generates an inhomogeneous dissipation of heat and
stresses around a crater which is irregular, different from the usual
circular cavity produced in Al2O3 or the fracture of glass insulators. That
model may be applied to other insulators and allow their tailoring for
new future high insulating applications.
3.2.2.2. Mechanical properties. Synthetic feldspar-based materials
generally have high mechanical strength and melting point, as well as
they are chemical inertness, for that reason literature has also paid
attention to their mechanical properties. The crystallized feldspar phase
is usually the main one, although, generally, there are other secondary
phases that form part of the ceramic or glass-ceramic based-materials
under consideration. Since most of the works are focused on the appli­
cation of these feldspar-based compositions for building materials, the
main properties that have been systematically studied are Vickers
microhardness (HV), elastic modulus (E), flexural strength (σ) and
fracture toughness (KIC). Very recently, tribological performance has
also started to be considered with the aim of designing functional feld­
spars with higher wear resistance suitable for high pedestrian traffic
applications. These properties are tabulated in Table 5.
In 1994 Barbieri et al. synthetized celsian and strontium-celsian glasses
and glass-ceramics by the well-known melting-quenching method and
devitrification, respectively. Glasses show HV values in the range 5.0− 6.9
GPa while glass-ceramics HV= 4.7− 6.9 GPa for celsian and HV= 5.3− 7.7
GPa for Sr-celsian, which evinces that Vickers microhardness decreases as
field strength of the associated cation decreases (Ca (0.33) > Sr (0.28) >
Ba (0.24)). Regarding E values, range from 57 GPa to 115 GPa in celsian
glass-ceramic and 90− 105 GPa in Sr-celsian glass-ceramic, showing a
good correlation with open porosity, increasing E values as porosity de­
creases. Furthermore, the sintered glass-ceramics present a larger KIC
because of pores, 2− 5 vol. %, and crystalline phase favor crack path de­
viation regarding the corresponding glasses, making sintering a good
toughening mechanism [194]. Between 2005 and 2009, Bernardo et al.
reported feldspar-based glass-ceramics crystallized from industrial waste
glasses and sintered below 950 ◦ C [17,64,66–69,215,216]. Glass-ceramics
sintered at 930 ◦ C for 3 h, with nepheline as major phase, followed by
celsian phase apart from other minority phases, showed remarkable me­
chanical properties that improved considerably after being reinforced with
Al2O3 platelets, obtaining the best σ, E and HV reported values for a
feldspar-based material for a reinforcement of 15 vol.% (Fig. 5 and
Table 5) [69]. Moreover, sanidine-based glass-ceramics were obtained
from industrial wastes (panel glass from dismantled cathode ray tubes,
mining residues from feldspar excavation and lime from fume abatement
systems of the glass industry). In terms of mechanical properties, they
showed HV up to 7 GPa at 5 N of load (Fig. 5a), σ values up to 120 MPa
(Fig. 5b), and E up to 81 GPa [64,215]. Following the same approach,
sanidine-wollastonite, sanidine-trikalsilite and albite-wollastonite-
trikalsilite based glass-ceramic were sintered at 880− 930 ◦ C and holding
times between 0–5 h, with bending strength values up to 79 MPa, 109 MPa
and 74 MPa, respectively, and Young’s modulus of 70− 100 GPa [216].
However, these materials are sintered at lower temperatures and times
than traditional ceramics, and, therefore, it might be suitable for the
production of building materials at very low cost. In 2008, they prepared
microcline-orthoclase glass-ceramics reinforced with Al2O3 platelets at
very low temperature (750 ◦ C). Glass-ceramics with the reinforcement of
15 vol.% of Al2O3 platelets enhance their mechanical properties, between
25–27 % for E, HV (Fig. 5a) and KIC, while, up to 55 % for σ (Fig. 5b) [17].
The behaviour of fast-sintered plagioclase-based glass-ceramics such as
labradorite (Na0.4Ca0.6Al1.6Si2.4O8) [66] and bytownite

Table 5
Mechanical properties for different feldspar-based materials of literature, indicating the type of material; glass (G), glass-ceramic (GC) or ceramic (C) and the evaluated
property: flexural strength (σ), elastic modulus (E), Vickers microhardness (HV), fracture toughness (KIC) and wear rate (Wr). Tabulated values for HV are at the load for
which those values are the maximum ones for the material under consideration. All the values are for 5 N, except in 1 (at 0.1 N) and 2 (at 0.5 N). See discussion of
Section 3.2.2.2 for more details about experimental conditions of test and composition.
Nomenclature Σ (MPa) E (GPa) HV (GPa) KIC (MPa m0.5) WR (mm3/N m) Ref.

G – – 5.0− 6.9 –
Celsian1 – [194]
GC – 57− 115 4.7− 6.9 –
1 G – – 5.0− 6.9 –
Sr-celsian – [194]
GC – 90− 105 5.3− 7.7 –
Celsian-based + x vol.% Al2O3 platelets (0 ≤ x ≤ 15) GC 120− 163 105− 122 6.6− 10.4 1.5− 1.9 – [69]
GC 120 81 7 – – [64]
GC 74 70 6.4 – – [215]
Sanidine-based
GC 79 77 – – – [216]
GC 109 71 – – – [216]
Albite-based GC 74 61 – – – [216]
Microcline/orthoclase + x vol.% Al2O3 platelets (0 ≤ x ≤ 15) GC 77− 119 62− 78 7.2− 8.9 1.5− 1.9 – [17]
Labradorite-based GC 108 82 7.2 1.6 – [66]
Bytownite-based GC 130 89 6.3 – – [67]
Plagioclase-based GC 133 126 7.3 – – [68]
GC 104 – – – – [79]
C 145 – – – – [71]
Anorthite-based C 82 – – – – [218]
GC 110 – – – – [217]
C – – 5.5 – – [226]
GC 75 – – – – [84]
Anorthite porcelain
GC 65 – – – – [219]
Albite G – 65 0.7− 0.9 – – [185]
Micro-nanostructured Na-rich plagioclase2 GC 83 78 9.5 2.1 6.1 10− 6
[22]
•

Micro-nanostructured anorthite-based2 GC 111 77 9.3 1.9 5.8 10− 6

[22]
•

315
V. Fuertes et al.
be extracted from Section 3.2.2.2, as well as Table 5. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of
this article).
(Ca0.85Na0.14Al1.83Si2.16O8) [67], using waste glasses as precursors, was
also studied. In the first case, bending strength values up to 108 MPa,
elastic modulus up to ~82 GPa, HV ~7.2 GPa at 5 N and KIC up to 1.64
MPa m0.5 at 30 N were obtained. In bytownite-based glass-ceramic,
bending strength values up to 130 MPa, elastic modulus up to 89 GPa, HV
= 6.3 GPa at 5 N. In these works, it is demonstrated the feasibility of
producing low-cost feldspar-based glass-ceramics with considerable me­
chanical properties, both from cheap precursor materials and the
fast-sintering process employed, which was at ~1000 ◦ C for 30 min with a
rapid cooling of 20 ◦ C/min. Finally, in 2009, they obtained a glass-ceramic
with plagioclase crystallizations (Ca/Na- feldspars), apart from pyroxenes
and wollastonite, from a vitrified mixture of important inorganic waste
(red mud, fly ash from lignite combustion and residues from the polishing
of porcelain stoneware tiles). It is observed that longer thermal treatments,
independently of heating mode, increase the amount of crystals and
consequently mechanical properties, reaching bending strength values up
to 133 MPa, elastic modulus of ~126 GPa and HV = 7.3 GPa at 5 N [68].
Taskiran et al. synthetized anorthite-based stoneware suitable for stone­
ware industry, with twofold flexural strength values than commercial
stoneware products, up to 110 MPa, by increasing the amount of anorthite
crystalline phase up to ~52 wt. % (72 wt. % of crystalline phase), while
conventional materials only contains around 28 wt. % of anorthite (~35
wt. % of crystalline phase) [217]. In 2012, Cheng et al. reported high
flexural strength values up to 104 MPa for anorthite ceramics obtained by
using feldspars as mineral raw materials as starting materials as well as
ball clay, quartz and calcite [79]. In 2014 Qing et al. obtained
anorthite-based ceramics by solid-state method with a σ up to 145 MPa, in
the range of typical values of LTCC materials [71]. Pal et al. evaluated the
flexural strength of anorthite porcelains with different degree of crystal­
linity for cooking wares, synthetized by using potassium feldspar, quartz
and aluminous cement as raw materials, reaching values of up to 75 MPa
for the sample with larger crystallinity, ~ 63 wt. % [84]. In 2017 Choi
et al. formulated an anorthite-based ceramic, formulated from kaolin and
calcite and different sintering aids such as feldspars, talc, frit or kaolin and
wollastonite, as calcium source with the aim of suppressing sintering
deformation. The use of kaolin/wollastonite in a ratio 1:1, leads to obtain
anorthite as a single phase with a lower shrinkage rate than commercial
materials, ~6 %, and σ up to 82 MPa [218]. In 2018, Arastehnodeh et al.
obtained anorthite porcelains by using white cement as a source of calcium
oxide, with σ values up to 65 MPa [219]. In 2019, Tangboriboon et al.
analyzed an anorthite porcelain where eggshells were used as raw mate­
rials as a calcium source for bio-dental and medical applications, reaching
values of E up to 47 MPa, a compressive strength of 978 MPa and a HV of ~
316
Journal of the European Ceramic Society 42 (2022) 307–326
Fig. 5. Selected mechanical properties of in­
terest in ceramic industry for different feldspar-
based materials of literature: a) Vickers micro­
hardness (HV) at 5 N of load and b) flexural
strength (σ). The feldspar-based ceramic fam­
ilies are grouped by colors: sanidine-based
(dark yellow) [64,215,216], plagioclase-based
(orange) [66–68], micro-nanostructured
plagioclase (blue) [22], celsian based (violet)
[69], microcline/orthoclase (green) [17],
albite-based (pink) [216], and anorthite-based
(red) [65,71,76,79,217,218]. All tests are car­
ried out by four points flexural method except
for micro-nanostructured plagioclase,
albite-based and anorthite-based ceramics,
which were measured by three points flexural
method. Different materials within a
feldspar-based composition are plotted with
different filled symbols. Empty symbols repre­
sent the same material with a reinforcement of
15 vol. % of Al2O3 platelets. Further details can
9 GPa at 1 N of load [221].
Feldspar-based porous ceramics have been also considered in liter­
ature. In 2018, Wang et al. obtained porous aluminum titanate‒stron­
tium feldspar‒mullite fiber (ASM) composite ceramics by a
conventional reactive sintering method, with flexural strength values up
to 26 MPa [220] In 2019, Zong et al. prepared anorthite-based porous
ceramics by using high-alumina fly ash microbeads and steel slag as raw
materials and sintering at 1120− 1200 ◦ C. They studied the flexural
strength in ceramic samples with different porosity from ~ 1 % to 50 %.
As sintering temperatures increased, porosity decreased and conse­
quently σ values were higher. In particular, σ values of ~ 5− 60 MPa
were measured [222]. Moreover, Al-Qahi et al. showed that two-stage
sintering process is a suitable approach to prepare high-performance
feldspar-based porous ceramics with high porosity [223]. After opti­
mizing sintering parameters, they obtained samples with an apparent
porosity up to 51.3 %, and compressive high strength up to 25.1 MPa.
Recently, Fuertes et al. [22,224] carried out a thorough character­
ization, at loads of 0.5− 10 N, of the engineered feldspar-based glass-­
ceramics previously mentioned in Section 3.2.2.1. The combination of
high crystallinity, low porosity and a novel engineered
micro-nanostructure developed by a fast sintering route lead the authors
to propose them for their application in high transit areas, because of the
good mechanical performance exhibited. Flexural strength values up to
111 MPa and Vickers microhardness values up to 9.5 GPa (at a load of
0.5 N) were measured, which supposed an enhancement of ~60 %
related to current glazes used in ceramic floor tiles for high transit areas.
Authors showed that the hierarchical micro-nanostructuration favours
crack deflection, reducing the brittleness and consequently increasing
KIC up to 2.1 MPa m0.5 (at 10 N) in these materials, which supposes an
increase of ~40 % regarding a standard glaze. Tribological properties
were also evaluated, as first time in feldspar-based ceramics, showing
that nanocrystals work as solid lubricants, favouring body sliding over
their surface and, consequently, reducing remarkably the damage suf­
fered, the friction coefficient and the wear rate (WR) up to 6∙10− 6
mm3/N m, half order of magnitude lower concerning the second best
reported value for a glass-ceramic for such applications (Fig. 6a) [22].
Alternatively, these authors deepen in the mechanical properties of the
engineered Na-rich plagioclase-based glass-ceramic, carrying out impact
tests (Fig. 6b) and measuring the resilience coefficient, comparing them
with the behaviour of a conventional glaze (Fig. 6c and d) [225]. From
this study, it was observed that the hierarchical micro-nanostructure of
the material favours stress relaxations, increasing impact resistance
regarding a conventional glaze and avoiding damages on its surface
V. Fuertes et al.
(Fig. 6b), while a conventional one suffers great flaking at the same load
(Fig. 6d).
Moreover, it has been also recently considered the preparation of
anorthite ceramics by using Spark plasma sintering (SPS) which allows
attaining high densification due to the implementation of pressure
during the sintering as well as lower firing times. Csáki et al. obtained
anorthite ceramics, sintered in the temperature range 850− 1100 ◦ C by a
heating rate of 50 ◦ C/min and dwell time of 10 min [226]. The pressure
applied was 50 MPa, before and during the heating. They observed that
samples prepared at 1100 ◦ C contained 90 wt.% of anorthite, while in a
sample sintered by conventional firing only 47 wt.%. of the anorthite
content is achieved. Consequently, anorthite by SPS shows HV values of
5.5 GPa at 5 N of load while the sintered conventionally 2.9 GPa.
Taking into account the recent advances and the current progress in
this field, it would be interesting to explore the micro-nanostructural
engineering in novel feldspar-based compositions, apart from plagio­
clases [22,224], since the presence of nanostructured microstructures
has been proved as a very effective tool to boost mechanical properties.
Considering at the same time fast sintering treatments at relatively low
temperature, could be a suitable approach to follow, as it has been
demonstrated, in order to obtain environmentally friendly densified
materials with promising mechanical properties for potential future
applications. One venue that has been opened through these works is
within the framework of high transit areas applications. Despite the
importance of wear properties in ceramics for such applications, it is a
property that has been hardly considered in literature (Table 5). Thus,
once nanostructured feldspar-based materials have been proposed as
excellent candidates for it, as well as the addition of hard phases as
reinforcement, this might be an interesting route to explore in future
investigations of this field. The attainment of feldspar-based materials
by using environmentally friendly starting raw materials has also been
evinced as a good path to be followed; however, future works in this
direction should optimize preparation methods to avoid the formation of
secondary phases that reduce the mechanical performance, for instance,
wollastonite, which is a common phase that appears in sintered ce­
ramics. Wollastonite has a Mohs hardness of 5 while plagioclases, for
instance, has a value of 7 [66]; and therefore hardness of the
feldspar-based material is reduced by its presence. Overall, taking into
consideration the different aspects presented above, the increase of
crystals, the reduction of its size and the enhancement of microstructural
homogeneity, should lead to improve crack deflection phenomena at
interfaces between glassy phases and crystals and consequently,
increasing the mechanical performance.
317
Journal of the European Ceramic Society 42 (2022) 307–326
Fig. 6. a) Modeled micro-nanostructured glass-
ceramic after wear test, showing a hardly non-
damaged surface thanks to the sliding favored
by nanocrystals which work as solid lubricants.
b) Images after an impact test of the same glass-
ceramic show that its surface is not damaged. c)
Modeled standard glaze after wear test,
showing a damaged surface with wear grooves
because of the large material spalling. d) Im­
ages after an impact test of the standard glaze
show that its surface is damaged and present
great flaking. Figures a) and c) are extracted
from [22] and b) and d) from [225].
3.2.2.3. Optical properties. Initial studies, in the last century, about
optical properties of synthetic feldspars were very systematic and
mainly based on characterization of their refractive index to contrast it
with the corresponding one in the natural counterparts. Owing to the
good mechanical performance that feldspar-based material exhibit, as it
has been previously discussed in Section 3.2.2.2, one of their main ap­
plications is in ceramic tile industry. Therefore, most of the works that
deal with optical properties of feldspar-based materials for that appli­
cation field are systematic, and study properties like their color co­
ordinates to verify that the aesthetic demands of the ceramic market are
satisfied. In the current century, the application area is broadened to­
wards luminescent applications, as it has been demonstrated by a large
number of works which show both intrinsic and induced emissions by
rare-earth (RE) elements in feldspar structures.
Goldsmith measured the refractive index (n) of synthetic albite,
potash and anorthite glass feldspars and their change after substituting
Ge and Ga by Si and Al in the tetrahedral positions of feldspar framework
[227]. The substitution of heavier elements in the structure of ternary
elements, considerably increased refractive index. Albite glass changes n
from 1.489 to 1.519, 1.592 and 1.636 in gallium albite (NaGaSi3O8),
germanium albite (NaAlGe3O8) and gallium-germanium albite (NaGa­
Ge3O8), respectively. In the case of KAlSi3O8 glass, refractive index shifts
from 1.488 to 1.513, 1.578 and 1.617 in gallium orthoclase (KGaSi3O8),
germanium orthoclase (KAlGe3O8) and gallium-germanium orthoclase
(KGaGe3O8), respectively. Finally, for anorthite glass, n changes from
1.575 to 1.633, 1.658 and 1.745 in gallium anorthite (CaGa2Si2O8),
germanium anorthite (CaAl2Ge2O8) and gallium-germanium anorthite
(CaGa2Ge2O8), respectively. Eskola et al. studied refractive index values
in the three-dimensional space (nx, ny, nz) in artificial alkaline-earth
feldspars synthetized by solid-state method in order to investigate
possible differences in their optical properties. They found that anorthite
and Sr-feldspars have n ~ (1.576, 1.584, 1.588) and, therefore, the same
optical properties, while Ba-feldspar register larger values, (1.587,
1.593, 1.600) [228]. Flehmig also studied the refractive indexes in the
three-dimensional space (nx,ny,nz) for gel grown feldspars with different
composition and Si/Al order/disorder. K-feldspars, both monoclinic
(1.518, 1.522, 1.523) and microcline (1.517, 1.521, 1.524), exhibited
the lowest values. The study revealed that albite showed slight varia­
tions with the Si/Al order/disorder, as reflects the analysis of low albite
(1.528, 1.532, 1.538) and intermediate albite (1.528, 1.533, 1.537). In
the case of plagioclases, they undergone an increase of n = (nx,nz) with
the rise of anorthite content, as shown the measurements in oligoclase,
An20 (1.538,1.545) and andesine An38 (1.548,1.556) [16].
As it was discussed in Section 3.2.2.2. feldspars are one of the main
V. Fuertes et al.
crystallizations that take part in ceramic tiles. Apart from the quality of
the products, it is necessary to satisfy the aesthetic demands of ceramic
market which pursue a great whiteness in them and, therefore, their
color coordinates have been also considered in more recent works to
evaluate it (Table 6). All the studied compositions are based on anorthite
crystallizations, as major phase. In 2005, Taskiran et al. obtained
anorthite-based stoneware with anorthite, ~52 wt.%, and glassy phase,
~28 wt.%) [217]. In 2012, Cheng et al. reported anorthite ceramics with
higher crystallinity, translucency and whiteness [79]. Both
anorthite-based materials present the typical lamellar crystals charac­
teristic of anorthite phase, however, in 2017, Enriquez et al. [23]
improved that whiteness, in an anorthite-based glass-ceramic tile pre­
viously mentioned, thanks to the singular micro-nanostructure devel­
oped. The increase of interfaces raises the light scattering, and leads to
this performance (Table 6), showing that microstructural engineering is
also a very powerful tool to tailor the optical behavior of feldspar-based
ceramics.
Moreover, authors evaluated reflectance of these materials in the
UV–vis- near infrared (NIR), obtaining average values of 47 %–85 % - 82
%, and 55 %–84 % - 88 %, for glass-ceramic tile and powder, respec­
tively. Albedo (solar reflectivity) was also evaluated, obtaining values of
85 % in the anorthite-based glass-ceramic powder and 84 % in the
corresponding tile form. The high albedo of the feldspar-based glass-
ceramic is comparable with the albedo of a commercial reflective paint
and about 7 % larger than a standard glaze of the ceramic sector. The
engineered micro-nanostructure of the glass-ceramic allows a larger
reflectivity in the NIR, which is translated into a lower heating of the
surface and makes it a strong candidate for cool roof applications [23].
On the other hand, there are a large amount of works in literature
that demonstrate the luminescent behavior of natural feldspar
[229–239], both, due to inherent emissions derived from structural
defects (mainly Al-O− -Al, Si-O− -Si, [AlO4∕alkali+] or [AlO4]◦ defects)
and from activator elements incorporated in their structure such as
rare-earth (RE) cations (Eu2+, Eu3+, Sm3+ or Ce3+, among others) or
transition metals (mainly Ti3+, Mn2+ and Fe3+) [240].Based on this,
several studies about photoluminescence in synthetic feldspars have
arisen in the current century, principally in alkaline-earth feldspars. A
deep study about luminescence in synthetic feldspars goes beyond the
scope of the present paper, however, the main research axes within this
framework are stated below. For further information the reader is
addressed to the references specified hereafter. Although some works
only evaluate the suitability of certain activator ions in the feldspar
matrix under study (mainly, Eu2+,Eu3+, Dy3+, Mn2+, Ce3+, Tb3+, Sm3+
and Yb3+, among others) [85,89,93,128,149,157,170], the current
trend is the development of new feldspar-based materials suitable for
white light-emitting diodes (w-LEDs), with the aim of overcoming some
of the main problems that current w-LEDs present such as: thermal
quenching, a low colour rendering index (CRI), <80, and high correlated
colour temperature (CCT), >6000 K [112,113,241]. Since white light
might be obtained through combination of blue/yellow emissions or
blue/green/red emissions, in the literature, the single or multiple doping
with RE ions into the corresponding feldspar matrix is carried out to
attain those emissions. So far, these studies have been only performed in
alkaline-earth feldspar-based phosphors (anorthite, strontium and
barium feldspars) [96,97,107,111,113,114,189] On the other hand,
Table 6
Chromatic coordinates in CIE L*a*b* system for different feldspar-based mate­
rials of literature.
L* a* b* Ref.
Anorthite-based stoneware 91.05 − 1.31 4.85 [217]
Anorthite ceramic 94.37 − 0.54 1.92 [79]
Micro-nanostructured anorthite-based glass- 94.59 − 0.85 0.85 [23]
ceramic tile
Micro-nanostructured anorthite-based glass- 98.14 − 0.2 0.59 [23]
ceramic powder
318
Journal of the European Ceramic Society 42 (2022) 307–326
very recently, it has been demonstrated the feasibility of attaining blue
and red luminescence in Na-rich plagioclase glass-ceramics from struc­
tural defects of feldspar lattice, induced by structural disorder in Si–Al
distribution, as occurs in the natural counterparts. That luminescence
can be tuned in wavelength and intensity without the presence of any RE
activator, only through structural tailoring, which has opened a new
gate [21,242].
In this section, it has been evinced the versatility of feldspar-based
materials derived from their optical properties. Apart from the possi­
bility of satisfying and improving the aesthetic demands of ceramic tile
market, in terms of great whiteness, new opportunities have raised due
to the structural and microstructural engineering of feldspar-based
glass-ceramics, demonstrating their suitability for cool roof and RE-
free phosphor applications. Moreover, feldspar-based matrices are
ideal for hosting RE activators which has allowed the development of
new feldspar-based materials for w-LEDs applications, but still with low
performance. These new applications are in an early stage; however, it
has been shown that the field of feldspar-based ceramics is very prom­
ising for future potential optical applications.
3.2.2.4. Thermal properties. Early works about thermal behaviour of
synthetic feldspars are mainly focused on a thorough study of their
thermal expansion in order to extend this knowledge to the natural
mineral counterpart. The measurement of the linear thermal expansion
coefficient (α) is part of regular study to ensure that properties meet
technical specifications for applications such as ceramic substrates in
electronic applications or ceramic tiles. The α values for different kind of
feldspars, synthetized by different methods, are tabulated in Table 7.
Bahat measured the linear thermal expansion coefficient (α) in the
BaO-Al2O3-SiO2, SrO- Al2O3-SiO2 and CaO- Al2O3-SiO2 systems for both
glasses and their corresponding glass-ceramics. In the first case, α values
are almost identical, in the range 6.3–6.5⋅10− 6 ◦ C-1, indicating that is
more dependent of tetrahedral network than the alkaline earth
composition. For glass-ceramics, α considerably varies, in the range
7.1–9.2⋅10− 6 ◦ C-1, since it depends on factors such as the expansion of
residual glass and the displacive transformation, among others [188].
Henderson et al. studied the linear and volume thermal expansion co­
efficient (αV) for several synthetic disordered alkali feldspars (Or19, Or38
and Or100) up to 1000 ◦ C, hydrothermally synthetized and compared
them with previously reported values for synthetic Rb-sanidine [243]
and high albite [244]. They found that in monoclinic frameworks, as
potassium content increases, the linear and volume expansion co­
efficients of orthoclase decreases for all crystallographic axis [134].
Hovis and coworkers studied the coefficient of volume expansion in
akali feldspars obtained by cation exchange varying orthoclase content
in the solid solution and afterwards, in several AlSi3O8 feldspars
[165–167], with αV of 39.0⋅10− 6 ◦ C-1 in a Li-feldspar, 16.7⋅10− 6 ◦ C-1 in
Rb-sanidine, 16.0⋅10− 6 ◦ C-1 in Rb-microcline and 14.6⋅10− 6 ◦ C-1 in
buddingtonite [167], 31.2− 19.2⋅10− 6 ◦ C-1 in sanidine-analbite series
and 30.7− 18.6⋅10− 6 ◦ C-1 in microcline-low albite [166]. From these
studies, it was extracted the important conclusion that Al-Si order/dis­
order has barely effect in the thermal expansion of alkali feldspars.
Barium and strontium feldspars are technologically very interesting
materials on account of their good properties and, for this reason, there
are several works in literature dealing with them. Among them, it is
worth highlighting the low thermal expansion coefficient for the mon­
ocelsian polymorph which has leaded to researchers to investigate this
property in these materials processed by different methods and under
different conditions. Kobayashi and Inagaki examined the thermal
properties of Sr-feldspar ceramics obtained via solid-state reaction in
which by varying the temperature of thermal treatment, between 950 ◦ C
and 1200 ◦ C, the obtained Sr-feldspar polymorph can be choosen. The
much lower thermal expansion coefficient for Sr-celsian, α = 4.2⋅10− 6 K-
1
, than for hexacelsian, α = 10.6⋅10− 6 K-1, makes the monoclinic poly­
morph suitable for electrical applications [73]. Fue et al. synthetized
V. Fuertes et al. Journal of the European Ceramic Society 42 (2022) 307–326

Table 7 from mineral raw materials, attaining α values of 4.5⋅10-6 ◦ K-1 [84].
Following abbreviations are used: Solid-state (SS), Sol-gel (SG), Hydrothermal In some of the works of Bernardo and co-workers, principally focused
(H), cation exchange (CE). Melting-quenching (MQ) and devitrification (Dev.) on the study of mechanical properties and discussed in Section 3.2.2.2,
are used to attain a glass and a glass-ceramic, respectively, after solid-state thermal expansion is also evaluated. They prepared sanidine-based glass
synthesis. from industrial wastes with α = 9.5⋅10− 6 ◦ K-1, while in the corre­
Nomenclature α (C− 1) (⋅10- Tª range Ref. sponding glass-ceramic, with several secondary phases, is decreased to α
6
) (◦ C) = 7.4⋅10− 6 ◦ K-1, value similar to the register one in natural stones (like
SS granite and marble) and glass-ceramics for tile applications [64]. In their
6.5
Hexacelsian
(MQ)
25− 1000 [188] work [215], it is obtained a sanidine/wollanstonite glass-ceramic with
SS
7.4− 8.0 lower α, 5.8⋅10− 6 ◦ K-1, on account of the higher amount of sanidine
(Dev.)
SS phase, which has an α of typically ~4.0⋅10− 6 ◦ K-1. The thermal behav­
6.3 iour of plagioclase-based glass-ceramics was also studied, like labra­
(MQ)
25− 1000 [188]
Hexagonal Sr-feldspar SS
7.5− 9.2
dorite (Na0.4Ca0.6Al1.6Si2.4O8) with α in the range 7.1− 7.9⋅10− 6 ◦ K-1
(Dev.) [66] and bytownite (Ca0.85Na0.14Al1.83Si2.16O8) with α ranging from
SS 10.6 30− 900 [73]
8.7− 9.6⋅10− 6 ◦ K-1 [67]. Since albite glass is a relevant component in
SS 4.2 30− 900 [73]
Sr-celsian many ceramic compositions, being often used as liquid phase during the
SS 2.5 25− 500 [207]
(Ba,Sr)-celsian/hexacelsian SS 7.0− 15.5 25− 400 [245] sintering. Dal Bó et al. synthetized albite glass with high purity in order
SS
6.5 to study it and measured α in the range 6.2–6.6⋅10− 6 ◦ K-1 up to 650 ◦ C
Hexagonal Ca-feldspar + (MQ)
25− 1000 [188] [185].
traces of An SS
(Dev.)
7.1 On the other hand, Hofmeister et al. published interesting works
Orthoclase19 24.3 560− 995 about the study of transport properties at high temperature of LiAlSi3O8,
Orthoclase 38 H 19.9 20− 1000 [134] NaAlSi3O8, CaAl2Si2O8, KAlSi3O8 synthetic glasses and their melts and
Orthoclase 100 15.3 20− 1000 compared with the corresponding crystals, with the aim of extracting
Rb-sanidine CE 11.8 20− 905 [243]
some geologic implications [246,247]. They observed that thermal
High-albite H 15.3 25− 850 [244]
Anorthite-based porcelainised conductivity (k) of crystals decreases as temperature increases, while in
SS 5.1 25− 600 [217]
stoneware glasses k increases with it (Fig. 7a). Heat capacity (Cp) rises in both cases
SS 4.9 30− 300 [79] as a function of temperature, with a higher rate in glasses than in crystals
SS
4.7 (Fig. 7b). According to the expression k = ρCpD, thermal diffusivity (D)
(MQ)
Anorthite-based
SS
30− 300 [206] of these glasses decreases with temperature approaching to a constant
3.4 around 1000 K, as well as it was verified that Dcrystal>Dglass>Dmelt,
(Dev.)
SS 5.3 25− 300 [71] which is attributed to an increase of disordering. Moreover, compared to
Anorthite porcelain SS 4.5 25− 650 [84] the crystals, D of the glasses has weaker temperature dependence since
SS
Albite glass 6.3 50− 300 [185] Cp increase is counteracted by the decrease of k and density. Generally,
(MQ)
SS in all these feldspars, D is nearly constant with T, and k values are
9.5
(MQ) around 10 % lower than in the corresponding crystal or glass counter­
25− 450 [64]
Sanidine-based
SS
7.4 part. Thus, the melting of feldspars impedes heat transport by conduc­
(Dev.)
tion, which provides a positive thermal feedback that might promote
SS
(Dev.)
5.8 30− 380 [215] further melting in continental crust [247].
SS
Labradorite-based 7.1− 7.9 30− 380 [66]
(Dev.) 4. Conclusions, challenges and future prospects of feldspar
SS application in ceramic sector
Bytownite-based 8.7− 9.6 20− 500 [67]
(Dev.)

In this work, the use of feldspars in ceramic sector is thoroughly

reviewed, emphasizing in their application as synthetic feldspar-based
(Ba,Sr)-O-Al2O3–2SiO2 ceramics through solid-state, in which celsian
material. The traditional use of feldspars as raw materials is expected
and hexalcelsian phases coexist. It is observed that SrO addition stabi­
to continue growing in next years and, consequently, their production
lizes celsian phase and α values can be controlled in the range
which is highly motivated by the expecting increase in the demand of
~7− 16.0⋅10− 6 C-1 [245]. Recently, El-Kheshen et al. synthetized
ceramic tiles accounted on the expected increase in construction and
monoclinic Sr-feldspar-based composites through the solid-state reac­
residential replacement, especially in growing economies and an up­
tion through the sintering of Sr-cordierite ceramic/borosilicate glass
ward use of ceramic tile inkjet. However, the interest of feldspars goes
composite with very low α, in the range 2.5–3.5⋅10− 6 ◦ C-1 [207].
beyond they are the most abundant mineral in the earth’s crust and,
Anorthite-based materials have also been very studied in literature.
therefore, their application as synthetic material has been thoroughly
Taskiran et al. fabricated anorthite-based porcelainized stoneware with
discussed. The structural and compositional features, as well as their
considerable better properties than the conventional porcelainized
remarkable properties as natural mineral might be seized to develop the
stoneware. The lower α = 5.1⋅10− 6 K-1 against typical α values of
corresponding synthetic counterpart with novel and improved func­
commercial products, α ~7− 9⋅10− 6 K-1, makes it a good candidate for
tionalities, evincing that they are very promising materials for their use
stoneware industry [217]. Kumar et al. prepared an anorthite glass with
in application fields such as construction, electronic or optoelectronic
α = 4.7⋅10− 6 K-1. The addition of 30 vol% of cordierite to glass
sectors, among others. In terms of crystallization, a broad range of
composition leads to crystallization of anorthite-cordierite composite
feldspar compositions have been deeply studied in literature from last
ceramics suitable for LTCC applications with a low α, 3.4⋅10− 6 K-1, close
century and there are multiple suitable approaches for their synthesis.
to that of silicon, α = 3.1⋅10− 6 K-1 [206]. Qing et al. also synthetized
Methods such as solid-state reaction or glass-ceramic route are of
anorthite-based ceramics for LTCC applications with α = 5.3⋅10-6 ◦ K-1
particular interest for industrially scalable applications. Moreover, a
[71]. In 2012, Cheng et al. designed anorthite-based ceramic for table­
large number of works have also been focused on the functional char­
ware market with low values of α, 4.9⋅10-6 ◦ K-1 below 300 ◦ C, which
acterization of their properties. Among them, the most interesting re­
might be easily matched with applicable glazes α, 3–4.5⋅10-6 ◦ K-1 [79].
sults and promising properties are stated below:
Pal et al. prepared an anorthite porcelain for cooking ware bodies, only
In the field of feldspar-based dielectric ceramics, so far, highly

319
V. Fuertes et al.
Fig. 7. Comparison of a) thermal conductivity (k) and b) heat capacity (Cp) for different feldspar crystals (solid dots), glasses (open dots), and melts (solid lines).
Following abbreviations are used: Ab = Albite and An = Anorthite. Each composition is represented with a different color: albite in black; anorthite in orange; low
sanidine in blue and Li- feldspar in violet. Adapted from [247].
crystalline micro-nanostructured Ca- and Na-rich plagioclase-based
glass-ceramics have shown the best performance in DC current, showing
the largest dielectric strength at room temperature, >57 kV/mm, re­
ported for a ceramic insulator and withstanding up to 200 ◦ C, with
dielectric strengths of 30− 44 kV/mm. That superior performance is
possible by a microstructural engineering carried out through a fast-
sintering process at 1220 ◦ C for 6 min, <1 h of total duration, which
allows the crystallization of nanostructured regions that hinder electric
conduction. Regarding AC behavior, at low frequency, they exhibit the
lowest εr, 4.6, for a synthetic feldspar-based ceramics while keeping low
tanδ, ~10− 3 [24,214]. At high frequencies, new investigated composi­
tions based on Ga- and Ge-containing feldspars, seem to be very prom­
ising for microwave applications and LTCC technology. Owing to Ge-O
bonds are weaker than Si-O bonds, tetrahedral ordering kinetics is
increased in these feldspars and consequently heat-treatment are
decreased, regarding traditional MAl2Si2O8 feldspars (M = Ca,Sr, Ba), in
which the best performance is attained for long sintering times, ~40 h.
The best behavior is reported for BaGa2Ge2O8 ceramic sintered at 1100
◦
C for 12 h which shows Q × f values up to 106,400 GHz with τf of − 26
ppm/◦ C [30]. Although these less common feldspar-based ceramics
show great potential and sintering times and temperature are consid­
erably reduced, for industrial applications sintering times should be
even shorter. Therefore, future works in this field should be directed at
investigating various methods to improve crystallization through green
body preparation and sintering stage, in order to attain high densified
ceramics and simultaneously reducing dielectric losses as well as energy
costs.
In the field of synthetic feldspar-based ceramics for building mate­
rials, most of the works are quite systematic and have aimed at
enhancing ceramic tile mechanical properties by crystallizing several
phases with good mechanical properties or by the incorporation of a
reinforcing phase. Several works [17,64,66–69,215,216] have demon­
strated that it is possible the manufacture of feldspar-based glass-­
ceramics sintered at relatively low temperature, <950 ◦ C, from cheap
industrial waste glasses, with a remarkable mechanical performance.
Best reported results are exhibited by nepheline/celsian-based glass-­
ceramics with a reinforcement of 15 wt.% Al2O3 platelets, attaining σ
values of 163 MPa, HV = 10.4 GPa and KIC = 1.9 MPa m0.5 [69]. The
incorporation of the concept of micro-nanostructural engineering has
been alternatively introduced as a new way to boost mechanical prop­
erties of feldspar-based glass-ceramics, without any reinforcing phase,
simply by developing hierarchically regions. In these works, fast sin­
tered Na- and Ca-rich plagioclase glass-ceramics have shown
320
Journal of the European Ceramic Society 42 (2022) 307–326
outstanding values of HV up to 9.5 GPa and KIC = 2.1 M P⋅m0.5 [22,224].
Additionally, in these works it is evinced that nanostructured regions
play an essential role in enhancing tribological properties, since they
work as solid lubricants, reducing considerably the friction coefficient,
the wear rate and preventing them from surface flaking after highly
energetic impacts. These novel micro-nanostructured materials open a
new gate to design new feldspar-based materials for their application in
high transit area and, therefore, an interesting route to explore in future
investigations of this field would be to widen this smart microstructural
design to other feldspar-based compositions, within their great range,
taking into consideration the use of eco-friendly raw materials and
sintering treatments.
Regarding thermal studies in synthetic feldspar-based materials,
most of the works are intimately linked with their application as ceramic
substrates in electronic applications or ceramic tiles, for that reason the
works have been focused on the systematic study of thermal expansion
in order to meet the requirements of ceramic market. Consequently, a
wide range of alkali and alkaline-earth compositions have been inves­
tigated. Other works have dealt with transport properties, basically
based on the study of the three end-members. The microstructural en­
gineering in fast-sintered micro-nanostructured anorthite-based glass-
ceramic has allowed the increase of phonon scattering phenomena
leading to thermal diffusivity values as low as 0.17 m2/s [23]. Although
these experimental results have elucidated that engineered feldspars are
suitable for ceramic tiles with enhanced thermal comfort, phonon
propagation in micro-nanostructured feldspars have not been studied
deeply yet and new experimental and theoretical studies are needed.
Therefore, future emerging works in this field should be directed to
explore transport properties in new alkali and alkaline-earth engineered
feldspars in order to attain a broader and deeper understanding along
with a microstructural correlation that allow their tailoring to adapt
them for improved future applications.
Another very important area of research is the study of their optical
properties. Although there are some systematic studies that deal with
properties such as refractive index and whiteness, their application as
phosphor is the one that has aroused more investigations in the current
century. Literature has extensively studied the doped, co-doped and tri-
doped with a wide range of RE ion activators that can act as luminescent
centres in the feldspar-based hosts, being the current trend to develop
new feldspar-based materials for w-LEDs applications. So far, these
studies have been only performed in alkaline-earth feldspar-based
phosphors, demonstrating that they are suitable for that purpose.
Therefore, the consideration of alkali feldspars hosts for these
V. Fuertes et al.
applications should be a future direction of this field. Alternatively, very
recently, it has been demonstrated the feasibility of attaining blue and
red luminescence in Na-rich plagioclase glass-ceramics from structural
defects of feldspar lattice, induced by structural disorder in Si–Al dis­
tribution. That luminescence can be tuned in wavelength and intensity
by means of structural tailoring, without the presence of any RE acti­
vator [21,242]. Thus, the translation of these findings to other Na-rich
feldspar hosts among alkali and plagioclase groups should become in
an interesting future research field to develop novel rare-earth-free
phosphors with tuneable luminescence by a scalable and cost-effective
route.
Despite the great scientific progress achieved in the ceramic sector
during last years by the development of nanotechnology and nano­
science, the incorporation of nanostructured feldspars is relatively
recent and is a fairly unexplored field. Recent works have demonstrated
that in situ formation of nanostructured feldspar-based materials allows
developing new and enhanced functionalities through the microstruc­
tural engineering, which has improved considerably the current per­
formance of materials used in ceramic sector. Based on this, new
investigations have started to explore new processing methods to open
new fields of application and, for instance, by ceramic injection
moulding [248,249] which might pave the way to the attainment of
feldspar ceramics with complex shapes and high dimensional precision
that might be applied in future applications of ceramic sector. Moreover,
the incorporation of micro-nanostructured feldspars in Portland cements
increase their thermal efficiency [250,251]. Although this area of
research is still in an early stage, the recent works have established the
guidelines to convert engineered feldspars in promising candidates for
future ceramic industry and consequently, feldspar engineering has
become a highly interesting research field. Future trends might be ori­
ented to carry out such engineering to other feldspar compositions,
taking into account the great range of them among the solid solution of
alkali feldspars and plagioclases, as well as the cation modifications
introduced by some authors to these main feldspar groups, who consider
the replacement of elements such as Sr2+, Ba2+, Ga3+ and Ge4+ by Ca2+,
Al3+ or Si4+. One of the most important challenges is the scale of tech­
nology by cost-effective and reproducible methods, for which the recent
progresses of feldspars processed as glass-ceramics seem to have
addressed properly that issue. Simultaneously, the increase of theoret­
ical studies about felspars will help to complement the great number of
experimental studies carried out, attaining a better understanding of
their structural features and widening their applicability field [252,
253].
Therefore, the many unique advantages and outstanding properties
of feldspar-based materials elucidate their potential for current and
future applications in ceramic sector and it is highly likely that multiple
works will emerge to explore some of their unknown aspects, making
simultaneously significant efforts to improve the current state-of-the-art.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This research was supported by the Sentinel North program of Uni­
versité Laval, made possible, in part, thanks to funding from the Canada
First Research Excellence Fund. The corresponding author, V.Fuertes,
holds a Sentinel North Excellence Postdoctoral Fellowship. This work is
also supported by the MINECO project MAT2017-86450-C4-1.
321
Journal of the European Ceramic Society 42 (2022) 307–326
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