Article
Particle-Reinforced Ceramic Matrix Composites—
Selected Examples
Katarzyna Konopka
Citation: Konopka, K.
Particle-Reinforced Ceramic Matrix
Composites—Selected Examples. J.
Compos. Sci. 2022, 6, 178. https://
doi.org/10.3390/jcs6060178
Academic Editor: Francesco
Tornabene
Received: 27 May 2022
Accepted: 14 June 2022
Published: 19 June 2022
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations.
Copyright: © 2022 by the author.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
J. Compos. Sci. 2022, 6, 178. https://doi.org/10.3390/jcs6060178
Faculty of Materials Science and Engineering, Warsaw University of Technology, 141 Woloska St,
02-507 Warsaw, Poland; katarzyna.konopka@pw.edu.pl; Tel.: +48-22-234-8738
Abstract: This paper presents some examples of ceramic matrix composites (CMCs) reinforced with
metal or intermetallic phases fabricated by powder consolidation without a liquid phase (melted
metal). Composites with a complex structure, which are an advanced group of CMCs called hybrid
composites, were described in contrast to conventional composites with a ceramic matrix. In advanced
CMCs, their complex structures make it possible to achieve the synergistic effect of the micro- and
nanoparticles of the metallic, intermetallic, and ceramic phases on the composite properties, which is
not possible in conventional materials. Various combinations of substrates in the form of powder
as more than one metal and ceramics with different powder sizes that are used to form hybrid
composites were analyzed. The types of CMC microstructures, together with their geometrical
schemas and some examples of real ceramic matrix composites, were described. The schemas of
composite microstructures showed the possible location of the ceramic, metallic, or intermetallic
phases in composites. A new concept of an advanced ceramic–intermetallic composite fabricated
by the consolidation of pre-composite powder mixed with ceramic powder was also presented.
This concept is based on the selection of substrates, two metals in the form of powder, which will
form a new compound, intermetallic material, during processing. Metal powders were milled
with ceramic powders to obtain a pre-composite powder consisting of intermetallic material and
ceramics. In the next step, the consolidation of pre-composite powder with ceramic powder allows
the creation of composites with complex microstructures. Selected examples of real particle-reinforced
conventional and hybrid microstructures based on our own investigations were presented. In addition
to microstructures, the properties and possible applications of CMCs were analyzed.
Keywords: ceramic–metal composites; ceramic–intermetallic composites; microstructures;
hybrid composites
1. Introduction
Ceramic matrix composites (CMCs) are composed of a combination of two materials:
ceramics with metal or intermetallic material. In particular, the ceramic–metal system links
materials of different chemical and physical properties, including chemical bonds. Despite
these differences between ceramics and metals, which are not favorable in the fabrication
process of ceramic–metal composites, they have been investigated for many years, and
the basic knowledge about their structure, properties, and directions of development has
been well documented [1–4]. The most important reason for these studies is to elaborate
ceramic–metal composites with the desired properties, such as improved fracture toughness,
high hardness, and good mechanical (bending strength) and tribological properties [5–9].
Another interesting system is ceramic–intermetallic material. The composites of this system
also possess improved fracture toughness, high hardness, and good properties at high
temperatures [10–12].
The majority of CMCs are composed of two kinds of ceramic powder and reinforce-
ment. Depending on the ceramics, ceramic–matrix composites can be distinguished as
oxide and nonoxide materials. The present work focused on oxide ceramics as a matrix
https://www.mdpi.com/journal/jcs
J. Compos. Sci. 2022, 6, 178 2 of 18

of composites. Different shapes and sizes of ceramic and reinforcement particles were
used to produce CMCs. As a result, various sizes, shapes, and phase distributions of
the sintered materials were obtained. Moreover, in many ceramic–metal systems, new
phases (spinels, oxides) as reaction products of substrates during processing can also
appear [5–7,9]. This means that a complex micro-nano structure of composites can be
formed. As a consequence, it enables the opportunity to create a large variety of micro-
nano-structured combinations with a spectrum of known and as yet unknown properties.
For this reason, in recent years, advanced CMCs, called hybrid composites, have been
intensively elaborated and investigated.
Hybrid material is treated as a combination of two or more materials representing
complex structures with phases of various morphologies and sizes for specific engineering
purposes [8]. Hybrid ceramic–matrix composites can combine more than two materials,
for example, two ceramics with one metal or more than one with a complex structure
and improved properties. In such multiphase composites with complex structures, it is
possible to achieve the synergistic effect of the micro- and nanoparticles of the metallic
phase, new compounds and ceramic phases on crack propagation, fracture toughness, and
other properties, which is not possible in conventional materials.
As an example, the composite based on the Al2 O3 –Ni system with the addition of
TiC can be mentioned. In this composite, good hardness and improved fracture toughness
were obtained. The relative density of the composite was 98%. The Vickers hardness for
this ternary composite was equal to 25.6 GPa and 30% larger than monolithic alumina
prepared by the same method. The bending strength was improved up to 75% of the value
obtained for alumina [13]. These values are the result of the nanoparticles of Ni and TiC
located in the microstructures. Moreover, TiC was added as a semiconductor phase to the
composite microstructure with the aim of obtaining an electrical conductor composite [13].
More examples of advanced composites are presented in another review paper [9].
Such composites are advanced compared to conventional composites. The proposed
division of composites into two conventional and advanced groups is conditional. Conven-
tional composites can be interpreted as two-phase materials, the microstructures of which
are shaped by one ceramic and one reinforcement. In particular, for composites fabricated
by powder consolidation, the initial powders have a selected size and shape. In general, a
uniform distribution of reinforcement with the same size and shape of particles in a ceramic
matrix without a complex structure is expected. Such a distinction between conventional
and advanced CMCs was made in the present paper.
In this paper, advanced ceramic matrix composites with metal particles and an inter-
metallic phase fabricated by powder consolidation without the liquid phase (molten metal)
during processing were analyzed together with conventional composites. In particular,
potential types of micro-nano hybrid structures were presented. Their microstructures,
together with their geometrical schemas and selected examples of real ceramic oxide matrix
composites, were described.
The presented geometrical schemas of CMC microstructures were based only on
possible combinations of the initial sizes of ceramic and metal powders and their location.
The assumption was made that the changes in the initial size of the powders as a result of
some processing are not very significant; however, in some powder consolidation methods,
it can be an important issue. Pores, which are typical of the various powder consolidation
techniques, were also not included. It should be noted that when two or more substrates
with various powder sizes are used to prepare a composite, the pore size and distribution
are also more complex. In particular, when micro- and nanopowders are combined, two
kinds of pores, micro- and nanopores, can be expected in the structure. The proposed
geometrical schemas should be treated as a schematic representation of the types of the
possible microstructures of CMCs.
A new concept of an advanced ceramic–intermetallic composite fabricated by the con-
solidation of pre-composite powder mixed with ceramic powder was also presented. CMC
composites were fabricated based on our own experimental work, which was performed
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 3 of 20

A new concept of an advanced ceramic–intermetallic composite fabricated by the

J. Compos. Sci. 2022, 6, 178 consolidation of pre-composite powder mixed with ceramic powder was also presented.3 of 18
CMC composites were fabricated based on our own experimental work, which was per-
formed under the supervision of the author. Moreover, the properties and possible appli-
cations of CMCs were also analyzed.
under the supervision of the author. Moreover, the properties and possible applications of
CMCs were also analyzed.
2. Conventional CMCs
2.Ceramic matrix composites
Conventional CMCs with incorporation metal or intermetallic phase are com-
monly known, and most of them
Ceramic matrix composites are with
applied as engineering
incorporation metalmaterials [5–12]. These
or intermetallic phasecom-
are com-
posites, which can be called as conventional CMCs, are mostly two-phase
monly known, and most of them are applied as engineering materials [5–12]. These materials withcom-
uniform distribution
posites, which canofbe reinforcement. However,CMCs,
called as conventional gradedare composites are also fabricated.
mostly two-phase materials with
The uniform
knowledge distribution of reinforcement. However, graded composites documented
of their microstructures, properties and fabrication is well in
are also fabricated.
the literature. Phase composition and microstructures of classical CMCs depend
The knowledge of their microstructures, properties and fabrication is well documented in on the
ceramic-reinforcement
the literature. Phase system and method
composition of fabrication. of classical CMCs depend on the
and microstructures
Powder consolidation system
ceramic-reinforcement techniquesand are one of
method ofthe most popular methods of producing
fabrication.
bulk composite
Powdermaterials [6]. During
consolidation sintering
techniques of powders,
are one depending
of the most on the parameters
popular methods of producing
of this process,
bulk the phase
composite composition
materials as well
[6]. During as microstructure
sintering of powders, of bulk material
depending onisthe
formed
parame-
[5–7]. For a ceramic–metal system, the temperature and atmosphere of sintering
ters of this process, the phase composition as well as microstructure of bulk material are the is
key formed
factors creating microstructures and phase composition (Figure 1).
[5–7]. For a ceramic–metal system, the temperature and atmosphere of sintering
are the key factors creating microstructures and phase composition (Figure 1).

Figure 1. Diagrams showing key factors controlling microstructures and phase composition of
ceramic–metal composites.
Figure 1. Diagrams showing key factors controlling microstructures and phase composition of ce-
ramic–metal composites.
Microstructures of ceramic–metal or ceramic–intermetallic composites are mostly
composed of ceramic grains and metal or intermetallic particles. It is well known that
Microstructures of ceramic–metal or ceramic–intermetallic composites are mostly
the final properties of composites depend on the size of both phases ceramic grains and
composed of ceramic grains and metal or intermetallic particles. It is well known that the
reinforcement particles and the distribution of them. Starting from the micro-sized metal
finalpowder
properties of composites
in composite, depend
different onof
sizes the size particles
metal of both phases ceramic grains
and distribution and rein-
in ceramic matrix
forcement
can beparticles
achieved. andThethe size
distribution
of metalofparticles
them. Starting from thecan
in composite micro-sized metal
differ from thepow-
starting
der in
sizecomposite,
of the metaldifferent
powder.sizes
It of metal particles
depends and distribution
on the method of powderinconsolidation
ceramic matrix andcanform-
be achieved. The size of metal particles in composite can differ from
ing parameters. The agglomeration of metal particles occurs very often, and finally the starting size of the
the metal powder.ofIt metal
agglomerates depends on theare
particles method
located of in
powder consolidation
the ceramic matrix. and forming
Metal pa- can
particles
rameters. The agglomeration of metal particles occurs very often, and finally
be surrounded by ceramic grains as well as located at triple points or at ceramic grain the agglom-
erates of metal (Figure
boundaries particles2).are located composite
Moreover, in the ceramic matrix. Metal
microstructures withparticles can be of
mixed location sur-
metal
rounded by ceramic grains as well as located at triple points or at ceramic grain
particles is also possible [5–7]. The size of metal particles can be also reduced by mechanical bounda-
ries process
(Figure of2).powder
Moreover, composite
mixing or whenmicrostructures
the temperaturewith mixed location
of sintering excessedofthe
metal parti-point
melting
cles of
is metal.
also possible [5–7]. The size of metal particles can be also reduced by mechanical
In the second case, the size and distribution of metal particles will be controlled
process of powder
by sintering ofmixing
ceramicorpowder
when the temperature
particles. of sintering
Sintering excessed theofmelting
with participation point
the liquid metal
of metal.
phaseInmeans
the second case, the
that melted metalsizecan
andpenetrated
distribution of metal
between theparticles
ceramic will be controlled
powder particles and
by sintering of ceramic
finally fulfil powder
the pores particles.
in sintered bodiesSintering
[5,6,9].with
Quite participation of the liquid
often, such ceramics metal
as Al 2 O3 and
ZrO2 , together with some metals, e.g., Ni, W Mo, Fe, Ti, and Cu, are combined [5–7,9,11,12].
 phase means that melted metal can penetrated between the ceramic powder particles and
finally fulfil the pores in sintered bodies [5,6,9]. Quite often, such ceramics as Al2O3 and
J. Compos. Sci. 2022, 6, 178
ZrO2, together with some metals, e.g., Ni, W Mo, Fe, Ti, and Cu, are combined 4[5– of 18
7,9,11,12].

Figure 2. SEM images of ceramic–metal composites microstructures: (A) composite Al2 O3 -Ni,
Figure 2. SEM images of ceramic–metal composites microstructures: (A) composite Al2O3-Ni, uni-
uniform distribution of Ni particles in ceramic matrix; (B) composite Al2 O3 -Fe, Fe particles located
form distribution of Ni particles in ceramic matrix; (B) composite Al2O3-Fe, Fe particles located at
at triple points and at ceramic grain boundaries. Source: results obtained under supervision of
triple points and at ceramic grain boundaries. Source: results obtained under supervision of K.
K. Konopka.
Konopka.

Metal nanoparticles are also used to produce ceramic–metal composites. In the fab-
Metal nanoparticles are also used to produce ceramic–metal composites. In the fab-
rication process, metal nanopowder is mixed with micro or nanopowder of ceramics. As
rication process, metal nanopowder is mixed with micro or nanopowder of ceramics. As
a result, in the composite, metal nanoparticles are situated as separated particles sur-
a result, in the composite, metal nanoparticles are situated as separated particles sur-
rounded by ceramic grains, or at the ceramic grains boundaries as well as in triple points.
rounded by ceramic grains, or at the ceramic grains boundaries as well as in triple points.
Mo, Ni, Ti and other metals are used and mixed with ceramics such as Al2 O3 or ZrO2 .
Mo, Ni, Ti and other metals are used and mixed with ceramics such as Al2O3 or ZrO2.
Nanocomposites represent hard materials but with improving fracture toughness [6,14,15].
Nanocomposites
Compositesrepresent
combininghard materials
ceramics but with improving
and intermetallic phase have fracture
been alsotoughness
developed.
[6,14,15].
Intermetallic materials are commonly used as a matrix because such composites have
Composites
desired properties combining
such as lowceramics
density,andhighintermetallic phaseexcellent
melting point, have been alsoand
wear developed.
oxidation
Intermetallic materials are commonly used as a matrix because
resistance [10–12]. The incorporation of the intermetallic phase into the ceramic such composites have de-
matrix
sired properties such as low density, high melting point, excellent
allows us to improve properties such as yielding, toughness, flexural strength, hardness, wear and oxidation
resistance [10–12].and
wear resistance Thealsoincorporation of the intermetallic
other properties. For example,phase into theofceramic
composites the Al2matrixO3 -TiAl
allows
system usareto investigated
improve properties[10,12]. such
Al2 Oas yielding,
matrix toughness,
composites flexural strength,
incorporated with hardness,
NiAl or Ni3 Al
3
wear resistance and also other properties.
phases are also the subject of research [11,16]. For example, composites of the Al 2O3-TiAl sys-

tem are investigatedceramic

Conventional [10,12]. matrix
Al2O3 matrix
composites,composites incorporated
well described in thewith NiAl or
literature, Ni3Al
represent
phases are also the subject of research [11,16].
properties which are needed in many applications. For example, Al2 O3 with Ni creates
Conventional
constructional ceramic matrix
composites composites,
with superior well described
mechanical in the[17];
properties literature, represent
in particular, the
properties
nanocomposite which Al are2 Oneeded
3 -Ni, in
with many
its very applications.
low wear For
rate example,
and high Al 2O3 with
toughness, is Ni creates
considered
constructional
for wear-resistant composites
components withandsuperior
cuttingmechanical
tools [18]. Al properties [17]; in particular,
2 O3 -Ni composites are also applied the
nanocomposite
because of their Almagnetic
2O3-Ni, with its very[19].
properties low wear rate and high toughness, is considered
for wear-resistant
Interesting components
properties and andwide
cutting tools [18]. Al
applications 2Obe
can 3-Ni composites
obtained for theare Al
also
2 Oapplied
3 -Al sys-
because of their magnetic properties [19].
tem [20,21]. Owing to the high toughness, high thermal and electrical conductivity of Al,
Interesting
composites fromproperties
this system andcanwidebeapplications can be obtained
applied as internal combustion for engine
the Al2O 3-Al system
piston crowns,
[20,21]. Owing
connecting to the
rods, high compressors
turbine toughness, high andthermal
for bicycleandcomponents
electrical conductivity
[21]. Al2 O3 -Moof Al,compos-
com-
posites from
ites with this system
laminated can be have
structure appliedvery asgood
internal combustion engine
self-lubricating, pistonand
mechanical crowns, con-
tribological
necting rods,which
properties turbine compressors
give and for bicycle
them the possibility to becomponents
applied as [21]. Al2O3-Mo
structural composites
materials in high
technology
with laminated [22]. For thermal
structure have barrier
very good coatings and multifunctional
self-lubricating, mechanical devices, the mullite-
and tribological
refractorywhich
properties metalsgive
(Mothem Nb) the
composites
possibility aretoused [23]. ZrO
be applied and Ni make
as2 structural composites
materials in high for
application
technology as thermal
[22]. For thermal insulation
barriermaterial
coatings[24].and The combinationdevices,
multifunctional of ZrO2 the with Ni gives a
mullite-re-
material
fractory with high
metals (Mo Nb)strength and heat
composites areinsulation,
used [23].especially
ZrO2 andgradedNi make composite,
composites i.e.,for
porous
ap-
ZrO2 -(ZrO
plication + Ni) can
as 2thermal be used inmaterial
insulation aerospace engineering
[24]. for boltedofjoints
The combination ZrO2[25].
withZrO ceramics
Ni2 gives a
are also a good choice in medical applications, for example, in
material with high strength and heat insulation, especially graded composite, i.e., porous combination with stainless
steel [26]. ZrO2 -Ta is another ceramic–metal composite for restoration medicines [27].
Metals, especially Ti or its alloys, are added to bioceramics such as hydroxyapatite [28].
Additionally, Ti-Fe composite powder is added to hydroxyapatite to obtain bulk composite
for the load-bearing biomedical application [29].
Some applications desired graded materials which are called functionally graded
materials (FGM) [30–32]. Such structures have gradually distributed reinforcement particles
 J. Compos. Sci. 2022, 6, 178 5 of 18

which means that as a result of technological process a continuous change in properties

is obtained [31–33]. The final graded structure depend on the method of fabrication and
initial components especially their chemical composition size, shape and contribution
are important [33]. FGM can be applied as constructional and functional materials. For
example, as thermal barriers, turbine blades, tools for plastic forming in automotive and
aerospace industries as well as biomaterials or optoelectronic materials [30–34].
Various methods can be used to create FGM structures. It can be listed infiltration
method, laser sintering, laminating, powder injection molding, electrolytic deposition,
plasma sintering, centrifugal slip casting, slip casting with using the magnetic field and
others [34–41]. In our own research for fabrication of graded ceramic matrix composites,
the following methods were used: slip casting (gravity gradient), slip casting with magnetic
field operation, centrifugal slip casting as well as additionally with magnetic field. As
a result, non-random distribution of metal particles was obtained. Moreover, the metal
particles concentrated close to each other and made chain patterns, as presented in Figure 3.
The presented microstructure of Al2 O3 -Ni composite was obtained by the slip casting
method with the use of magnets during processing. At the top of the sample, the Ni
particles were uniformly distributed into the ceramic matrix (Figure 3A). At the bottom
of the sample, where the magnet was placed, the concentration of Ni particles was higher
and a chain pattern was formed (Figure 3B). Our own research considered such systems as
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 6 of 20
Al2 O3 -Ni, Al2 O3 -Mo, Al2 O3 -Cu, Al2 O3 -W and also ZrO2 -Ni [42–45]. Graded composites
can be also multiphase materials with complex structures; however, their processing is
more complicated than classical two-phase composites with graded distribution of them.

Figure 3. SEM images of Al2 O3 -Ni graded composites, graded concentration of Ni particles obtained
Figure 3. SEM images of Al2O3-Ni graded composites, graded concentration of Ni particles obtained
byslip
by slip casting
casting method
methodwithwithuse
useofof
magnet:
magnet:(A)(A)
top top
of sample, random
of sample, distribution
random of Ni particles;
distribution of Ni particles;
(B) bottom of the sample where the magnet was, with Ni particles close to eachand
(B) bottom of the sample where the magnet was, with Ni particles close to each other chain
other and chain
patterns are visible. Source: results obtained under supervision of K. Konopka.
patterns are visible. Source: results obtained under supervision of K. Konopka.

3. Advanced CMCs
Although the conventional ceramic matrices are commonly fabricated and most of
them are applied, still there is a need to elaborate new advanced composites with a ce-
J. Compos. Sci. 2022, 6, 178 6 of 18

3. Advanced CMCs
Although the conventional ceramic matrices are commonly fabricated and most of
them are applied, still there is a need to elaborate new advanced composites with a ceramic
matrix. Advanced CMCs are based on conventional composites, the known rules of shaping
their structures and properties. However, the development of advanced CMCs demands
new concepts of design and fabrication of desired microstructures and properties. The
new concepts of advanced composites include multiphase and complex structures called
Figure 4. SEM images of ceramic–metal composites microstructure represent type IA from Table 1;
hybrid
Figure [8]. In hybrid
4. SEM images CMCs, various variants
of ceramic–metal composites of combining
microstructure ceramics
representwithtypemetals
IA fromand also1;
Table
Al 2O3‐Ni, Ni particles (white) located in ceramic matrix. Source: results obtained under supervision
intermetallic
2O3‐Ni, Ni phases
AlK. particlesare possible,
(white) locatedas in
opposed
ceramic to conventional
matrix. CMCs,
Source: results in which
obtained there
under is only
supervision
of Konopka.
one ceramic
of K. Konopka. and one reinforcement composed of microstructures.
One example
Ternary system of such composite
composites, linkstwo
where a ceramic
ceramics matrix
are with one metal
combined withbut is located
metal, or one
inceramicTernary
a matrix in system
the form composites,
of both micro where
and two ceramics
nanoparticles. are
To
with two metals, or other combinations also with intermetallic compounds, combined
prepare such with metal,
composites, ortwo
one
also
ceramic
metal with
powders two
canmetals,
be used, or other
one combinations
with micro and also with
the second
belong to the new composites with complex structures. There are papers describing the intermetallic compounds,
with nanoparticles. also
These
metal
belong powders
to the can be combinedwith with micro or structures.
nanoparticles of ceramic powder particles.
composites of new
ternary composites
systems such complex as ZrO2‐Ti‐Ni [46] or There are papers
Ni‐Ti‐ZrO describing
2 [47]. Results sug‐
the
Such combinations
composites of ternaryof ceramic and metal powders and their consolidation provide us with
gested that the additionsystems such substrate
of one more as ZrO2‐Ti‐Ni [46] an
provides or Ni‐Ti‐ZrO [47]. Resultsprop‐
increase in2 mechanical sug‐
various
gested options
that the ofaddition
microstructures.
of one Thesubstrate
more geometrical schemas
provides an of predicted
increase in microstructures
mechanical prop‐
erties with respect to the two substrates in composites obtained by the same method. For
oferties
such with
CMCs are collected
respect to of
thethe in Table
two 1. An in
substrates example
compositesof a real microstructure
obtained by the same of composites,
method. For
example, composites Ni‐Ti‐ZrO 2 system are considered as anodes for high temper‐
type IA according
example, composites to Table
of 1, is
the presented2 system
Ni‐Ti‐ZrO in Figure are4.considered
In this selected
as example,
anodes for Ni powders
high temper‐
ature fuel cells, because both their mechanical properties and the anode performance are
with
aturedifferent
fuel sizes
cells, of micro-
because both and
theirnanopowders
mechanical were usedand
properties andthe
combined
anode with ceramic
performance are2
better than for those prepared in the same way but containing two components, Ni‐ZrO
micropowder.
better than 2for Bigger
those Ni particles
prepared are surrounded by ceramic grains, and smaller Ni
and Ti‐ZrO [47]. There are alsoinpapers
the same wayreport
which but containing
the resultstwo components, Ni‐ZrO
of investigations of com‐2
particles are situated at triple points and at the ceramic grain boundaries as well as of inside
and Ti‐ZrO
posites with Al2O3 matrix with the addition of ZrO2 and Ti(C,N) [48], Al2O3‐ZrO2‐Nbcom‐
2 [47]. There are also papers which report the results of investigations [49]
the ceramic
posites with grains
Al2O (Figure 4). For bigger Ni particles, deflection of
3 matrix with the addition of ZrO2 and Ti(C,N) [48], Al2O3‐ZrO2‐Nb [49]the crack is expected.
as well as three components such as Al2O3‐ZrO2‐CeO2 with the addition of Ni [50]. An‐
Crack
as welldeflection
as threeisby larger metalsuch
components particles Alas
aslinks 2Owell
3‐ZrO as2‐CeO
Ni were
2 withreported in the literature
the addition of Ni [50]. [5,6].
An‐
other
Small example
Ni particles a composite
effectively which
redirect or ZrO
stopZrO 2 with Al2O3 and (Ti,W)C [51]. These com‐
the2cracks [6].
other example is a composite which links
posites were fabricated by hot pressing or die pressing and sintering. with Al 2O3 and (Ti,W)C [51]. These com‐

posites were fabricated by hot pressing or die pressing and sintering.

Table 1. Types of microstructures of ceramic–metal composites fabricated by consolidation of pow-
Table 1. Types of microstructures of ceramic–metal composites fabricated by consolidation of pow‐
ders, one
Table 1. ceramic
Types ofand one metal with
microstructures various variants
of ceramic–metal of ceramicfabricated
composites and metalbypowder size andoftheir
consolidation
ders, one ceramic and one metal with various variants of ceramic and metal powder size and pow‐
their
geometrical
ders, one schemas.
ceramic
geometrical schemas.and one metal with various variants of ceramic and metal powder size and their
geometrical schemas.
Schema
Schemaofof
Matrix Matrix
ReinforcementReinforcement Schema of
Microstructure
MatrixType Reinforcement Microstructure
Type Ceramics Metal Microstructure
Type Ceramics Metal Metal Metal C1
Ceramics C1Metal M1 Metal M1 C1++M1M1++M1M1
C1 M1 M1 C1 + M1 + M1
C1 M1 M1

μm μm
µm µm nano nano
IA μm I A μm
(white) (red) nano
IA (white) (red) (red) (red)
(white) (red) (red)

μm
nano μm µm
nano
IB nano (red)
nano nano
IB (white)I B (red) (red) (red) nano
(white) (white) (red) (red)

Ternary system composites, where two ceramics are combined with metal, or one
ceramic with two metals, or other combinations also with intermetallic compounds, also
belong to the new composites with complex structures. There are papers describing the
composites of ternary systems such as ZrO2 -Ti-Ni [46] or Ni-Ti-ZrO2 [47]. Results suggested
that the addition of one more substrate provides an increase in mechanical properties with
respect to the two substrates in composites obtained by the same method. For example,
composites of the Ni-Ti-ZrO2 system are considered as anodes for high temperature fuel
cells, because both their mechanical properties and the anode performance are better
 J. Compos. Sci. 2022, 6, 178 7 of 18
Compos. Sci. 2022, 6, x FOR PEER REVIEW

than for those prepared in the same way but containing two components, Ni-ZrO2 and
Ti-ZrO2 [47]. There are also papers which report the results of investigations of composites
deflection
with Al2 O3by larger
matrix withmetal particles
the addition as2well
of ZrO as Ni were
and Ti(C,N) [48], Alreported in the
2 O3 -ZrO2 -Nb [49] literatur
as
well as three components such
Ni particles effectively redirectas Al O
2 or
3 -ZrO
stop
2 -CeO
the with the addition
2 cracks [6]. of Ni [50]. Another
example is a composite which links ZrO2 with Al2 O3 and (Ti,W)C [51]. These composites
were fabricated by hot pressing or die pressing and sintering.

Figure 4. SEM images of ceramic–metal composites microstructure represent type IA from Table 1;
Figure 4. SEM
Al2 O3 -Ni, images
Ni particles of located
(white) ceramic–metal composites
in ceramic matrix. microstructure
Source: results represent
obtained under supervisiontype IA
Al2O3-Ni, Ni particles (white) located in ceramic matrix. Source: results obtained unde
of K. Konopka.
of K. Konopka.
Composites consisting of three substrates such as one ceramic matrix and two metals
fabricated from initial powders, with their various initial sizes, can form complex mi-
Ternaryinsystem
crostructures which metalcomposites,
reinforcements where
can betwo ceramics
located as separatedareparticles,
combined at thewith m
grain boundaries of the ceramic matrix as well as inside the ceramic matrix grains. Accord-
ceramic with two metals, or other combinations also with intermetallic comp
ing to the size of ceramic and metal powders, the schemas of microstructures and location
belong to the new
of reinforcements composites
are presented with
in Table 2 (C1complex
+ M1 + M2). structures.
Moreover, There
the samearetypepapers
of de
composites
microstructures of represented
ternary systems
by schemassuchin Tableas 2ZrO 2-Ti-Ni
will be created[46]
throughor aNi-Ti-ZrO
combination2 [47].
of two ceramics, one as a matrix and a second as reinforcement,
gested that the addition of one more substrate provides an increase and metal as the nextin mech
reinforcement phase, which is presented in Table 2 (C1 + C2 + M2).
ertiesPresented
with respect in Tableto2 are
thegeometrical
two substratesschemasin of composites
microstructuresobtained
of CMCs basedby theon same
example, composites
possible combinations of of
onethe Ni-Ti-ZrO
ceramic powder2as system
a matrixare considered
combined with two asvarious
anodes for h
metals, or two ceramics and one metal with different sizes of
ature fuel cells, because both their mechanical properties and the anode perfinitial powders and various
location of phases at composites. Such combinations lead to models which are the same
better than for
geometrically. Thethose prepared
fact that schemas ofin the same way
microstructures are thebut
samecontaining
geometricallytwo does compone
not
and
meanTi-ZrO [47]. There
that the2 properties are also
represented papers
by these which report
microstructures are the the
same.results
However, oftypes
investigat
of microstructures
posites with Al2O and their schemas can be useful in the process of composite tailoring
3 matrix with the addition of ZrO2 and Ti(C,N) [48], Al2O3-Z
and prediction of their properties.
as wellTheas three own
author’s components
experiments,suchunderas theAl 2O3-ZrO2of
supervision -CeO 2 with
Konopka, theon
based addition
com- of
other example
posites with complexis a microstructures
composite which links ZrO
concentrating with
on the2 Al Al2Oand
2 O3 metal 3 andZrO(Ti,W)C
2 metal [51].
composites
posites were in which Ni, Ti and
fabricated byTihot
+Ni were used [52–55].
pressing or dieThe microstructure
pressing of ZrO2 -Ti-Ni
and sintering.
composite is presented in Figure 5A. Three phases are visible: matrix ZrO2 , Ti particles and
Ni particles. In the presented microstructure, the Ti and Ni phases are located as separated
Table 1. Types
by ceramic of microstructures
matrix of ceramic–metal
or located as neighbors. The nanometric composites
initial powderfabricated
of ZrO2 byandconsolid
ders, one ceramic
micrometric and
Ti and Ni one metal
powders withinvarious
were used fabricationvariants of ceramic
of composites. and metal powder
The microstructures
of ZrO
geometrical
2 -Ti-Ni composite
schemas. can be represented by the type IIE (Table 2), where one ceramic
matrix and two metals with various sizes of powders were combined.
Schema of
Matrix Reinforcement
Microstruc
ype
Ceramics Metal Metal
C1 + M1 + M
C1 M1 M1
 The second composite investigated in our own research system was Al2O3‐TiC‐Ti.
This system represents a combination of substrates as follows: two ceramics, one as matrix
of composite and the second one as reinforcement, and metal as another reinforcement.
In this combination, the various options of size of powder particles can also be considered.
In the presented composite, Al2O3 is a matrix and Ti and TiC particles are located in the
J. Compos. Sci. 2022, 6, 178 ceramic matrix (Figure 5B). The metal particles as well as their agglomerates are distrib‐ 8 of 18
uted in the ceramic matrix. However, chains of fine Ti particles were also found at the
TiC/Al2O3 interface (Figure 5B). The microstructure of this composite can be classified as
IIB in Table 2.
Table 2. Types of microstructures of ceramic–metal composites fabricated by consolidation of pow-
ders: one ceramic
Table and
2. Types two metals with
of microstructures various variants
of ceramic–metal of ceramics
composites andbymetal
fabricated powderofsize,
consolidation pow‐or
two ceramics and
ders: one one metal
ceramic with
and two various
metals variants
with various of ceramics
variants and and
of ceramics metal powder
metal powdersize
size,and their
or two
ceramics
geometrical and one metal with various variants of ceramics and metal powder size and their geomet‐
schemas.
rical schemas.
Schema of
Matrix Reinforcement Schema of
Matrix Reinforcement Microstructure
Microstructure
Type
Type Metal M1 Metal M1
Ceramics
C1 ++ M1
C1 M1 ++M2
M2
Ceramics or MetalMetal or
C1 or M2 or
C1 Ceramics C2M2 C1 + C2 + M2
Ceramics C2 C1 + C2 + M2

μm µm μm µm μm µm
IIA
J. Compos. Sci. 2022, 6, x FORIIA
PEER REVIEW 9 of 20
(white) (white)(blue) (blue) (black)(black)
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 9 of 20
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 9 of 20
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 9 of 20
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 9 of 20
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 9 of 20
μm µm μm µm nano nano
IIB IIB
μm
IIB (white)
μm (white)μm
(blue)
μm (blue) nano (red)
(red)
nano
IIB (white)
μm (blue)
μm (red)
nano
IIB (white)
μm (blue)
μm (red)
nano
IIB (white)
µm (blue)
µm (red)
nano
IIB (white) (blue) (red)
μm (white) nano(blue) (red)
nano
IIC μm µm nano nano nano nano
IIC (white )
IIC
μm (black)
nano (red)
nano
IIC (white ) (white)(black) (black) (red) (red)
μm
(white ) nano
(black) nano
(red)
IIC μm nano nano
IIC µm
(white ) nano
(black) nano
(red)
IIC (white ) (black) (red)
(white ) μm (black) (red)
nano μm nano
IID nano (blue)
μm nano
IID (white) µm (red) nano
nano
(white) nano (blue)
μm nano
(red)
IID IID
nano (blue) (blue) nano
IID (white) (white)μm µm
(blue) (red) (red)
nano nano
(white) nanonano
(red)
IID IID (blue)
(blue)
(white)
(white) (red)
(red)
nano μm μm
IIE nano μm μm
IIE (white)
nano (blue)
μm (black)
μm
IIE (white)
nano (blue)
μm (black)
μm
(white) nano (blue) µm (black) µm
IIE IIE
nano nano µm µm
IIE IIE (white) (white)μm
(blue) (blue) μm
(black) (black)
(white)
(white) (blue)
(blue) (black)
(black)
nano nano nano
IIF nano nano nano
IIF (white)
nano (black)
nano (red)
nano
IIF (white)
nano (black)
nano (red)
nano
IIF (white)
nano nano (black)
nano (red)
nano
IIF (white) nano nano
(black) nano nano
(red) nano
IIF IIF (white) (black) (red)
(white) (white)(black) (black) (red) (red)

Figure 5. SEM images of ceramic–metal composites microstructures: (A) composite ZrO2‐Ti‐Ni, ma‐
Figure 5. SEM images of ceramic–metal composites microstructures: (A) composite ZrO2‐Ti‐Ni, ma‐
trix 2 (light grey),
ZrOimages Ti particles (dark grey) and microstructures:
Ni particles (grey); (A) (B) composite AlZrO 2O3‐TiC‐Ti,
SEM
Figure 5.Figure 5.2 SEM of ceramic–metal
images of composites composite 2 -Ti-Ni,
trix ZrO
matrix Figure (light
AlSEM 5. SEM grey), Ti ceramic–metal
images particles (dark composites
of ceramic–metal grey) and Ni
composites microstructures:
particles (grey);
microstructures: (A) composite
(B)
(A) composite
composite
2O3 (dark grey), Ti particles (white), TiC particles (black). Source: results obtained under
ZrO
ZrOAl222‐Ti‐Ni,
O3‐TiC‐Ti,
-Ti-Ni, ma‐
ma-
Figure
matrix ZrO
trix2ZrO 5.
(light images
grey), Ti of ceramic–metal
particles (dark composites
grey) and Ni microstructures:
particles (grey);(A)
(B)composite
composite ZrO Al ‐Ti‐Ni,
O ma‐
-TiC-Ti,
2(light grey), Ti particles (dark grey) andandNiNi particles (grey); (B) composite Al 22O
2O33‐TiC‐Ti,
2
matrix trix
Al
supervision
2 ZrOO (light
3 2(dark
of K. grey),
grey),
Konopka. Ti
Ti particles
particles (dark
(white),grey)
TiC particlesparticles
(black).(grey); (B)
Source: composite
results Al
obtained -TiC-Ti,
3under
Figure
trix ZrO 5. SEM
2 2(light images
grey), of ceramic–metal
Tigrey),
particles (dark composites
grey) and microstructures:
Niparticles
particles (A)
(grey); composite
(B) composite ZrO ‐Ti‐Ni,
Al2O3‐TiC‐Ti,
2 ma‐
matrix
matrix Al 2 OZrO
Al
matrix
3 (dark
supervision O Al (dark
O
ofgrey),
3 K.grey),
2 3 grey),
(dark
TiTi
Konopka. Ti particles
particlesTi (white),
particles
(white), TiC
(white), TiCparticles
TiC particles (black).
(black).
(black). Source:
Source:
Source: results
resultsobtained
obtained
results obtained under
under
under
trix
matrix 2 (light
Al 2O3of(dark grey), particles (dark
Ti particles grey) and
(white), Ni particles
TiC particles (grey);
(black). (B) composite
Source: Al2O3‐TiC‐Ti,
results obtained under
supervision
supervision K.of Konopka.
K. Konopka.
supervision
matrixofIn K.
the
Al Konopka.
O group
(dark
supervision of K. Konopka.
2 3 of advanced
grey), Ti CMCs
particles are
(white), multiphase
TiC particles composites
(black). with
Source: new
resultsphases
obtained forming
under
In the
supervision
during the group of advanced
ofprocessing.
K. Konopka. CMCs
For oxide are multiphase
ceramics combine composites
with some with new spinel
metals phases phase forming or
In the Ingroup
the group of advanced
of advanced CMCs CMCs areare multiphase
multiphase composites
composites with
with newphases
new phases formingforming
during
metal the
oxides processing.
can be For
synthetizedoxide ceramics
during combine
process of with
sintering. someThey metals
are spinel
mostly phase
located or
at
during In the
during group
the processing. of advanced
the processing. For For CMCs
oxideoxide are multiphase
ceramics
ceramics composites
combinewith
combine withsome with
somemetals new phases
metals spinel
spinel phase forming
phase or or
metal
the Inoxides
the
ceramic/metalgroup can of be synthetized
advanced
interfaces. CMCs
In during are
particular, process
multiphase
the of sintering.
spinel composites
phase canThey
with are
surroundnewmostly
phases
the located
metal forming at
parti‐
during
metal metalthe
oxides processing.
oxidescan canbe For oxide
be synthetized
synthetized ceramics
during
during combine
process
process ofof with some
sintering.They
sintering. metals
Theyare spinel
aremostly
mostly located phase
located at or
at
the
clesceramic/metal
during the
[56,57]. processing.
Because interfaces.
aFor In particular,
oxide
ofinterfaces.
weaker ceramics the spinel
combine phase
thancan
with some surround
metals the interface,
spinel metal phaseparti‐
or
metal
the theoxides
ceramic/metal can be
ceramic/metal synthetized
interfaces. In Inspinel/metal
during
particular, process
particular,
the interface
the of sintering.
spinel
spinel phase
phase spinel/ceramics
They
can
can are mostly
surround
surround the metal
the located
metal af‐
at
parti-
parti‐
cles
metal
ter [56,57].
oxides
pulling Because
out can be
metal of a weaker
synthetized
particles, spinel/metal
during
voids very process
often interface than
of sintering.
exist in the spinel/ceramics
They are mostly
microstructures interface,
(Figure located af‐
at
6A,B).
the ceramic/metal
cles [56,57]. interfaces.
Because of a In particular,
weaker the
spinel/metal spinel phase
interface
cles [56,57]. Because of a weaker spinel/metal interface than spinel/ceramics interface, af‐ can
than surround
spinel/ceramics the metal
interface, parti‐
af-

J. Compos. Sci. 2022, 6, 178
The spinel is active in crack propagation. Cracks are mostly deflected by the spinel
phase [6,56,57,60]. In cases where all metal is transferred to the spinel phase, the compo-
sites consist of two phases, i.e., ceramics and spinel. The microstructure of this composite
can be considered as a typical classical two-phase composite. On the contrary, when both
spinel and metal are in the composite microstructure, various spinel locations 9 ofand
18 its

thickness can be noticed. As presented in Figure 6C, in composite Al2O3-Ni, the spinel
phase NiAl2O4 consists of fine grains surrounding the metal particles and does not have a
Theshape
regular second andcomposite
thickness. investigated in our own research
Such a microstructure system was
can be classified as aAl 2 O3 -TiC-Ti.
complex ternary
This system represents a combination of substrates as follows: two ceramics,
microstructure of composite where the ceramic is a matrix, and the metal and spinel phase one as matrix
of composite
are and theSuch
reinforcements. second one as reinforcement,
a complex microstructure anddepends
metal asonanother reinforcement.
the shape In
and distribution
this combination, the various options of size of powder particles can also be considered.
of the spinel, and there are no geometrical schemas of it in Table 2.
In the presented composite, Al2 O3 is a matrix and Ti and TiC particles are located in the
In the same group as the above-mentioned group of CMCs are composites in which
ceramic matrix (Figure 5B). The metal particles as well as their agglomerates are distributed
various oxides
in the ceramic of metals
matrix. are formed.
However, chains ofTheir
fine Tilocation
particles can
werecreate the complex
also found at the TiC/Almicrostruc-
2 O3
tures. Very
interface fine oxide
(Figure 5B). Theparticles can be located
microstructure at grain boundaries
of this composite of the
can be classified asceramic matrix
IIB in Table 2. as
well In
as the
at ceramic/metal interfaces and also inside the grains and
group of advanced CMCs are multiphase composites with new phases forming interlocked by ceramic
grains
during(Figure 6D). These
the processing. Forfine particles
oxide of oxides
ceramics combinecanwith
verysome
effectively
metalsstop spinelandphase
redirect
or the
crack
metal propagation.
oxides can beMoreover,
synthetized because
duringof their high
process hardness,They
of sintering. the effect of hardening
are mostly located can
be noticed.
at the Our own investigations
ceramic/metal of composites
interfaces. In particular, ZrO2-Ni
the spinel andcan
phase ZrOsurround
2-Ti, in which very fine
the metal
particles [56,57]. Because of a weaker spinel/metal interface than spinel/ceramics
oxides particles were identified, confirm this effect [53,54,57]. In particular, in the ZrO2-Ti interface,
after pulling
system, veryout metal
fine (100particles, voids Zr-Ti-O
nm) phases, very oftenand exist in the microstructures
precipitation of titanium (Figure 6A,B).
oxides ZrTiO2
Such a feature of spinel morphology, i.e., an oval shape with a hole
were located in the ceramic matrix [49]. This composite geometrical schema of a micro-inside, which can be
called “doughnut”
structure shape, was
can be considered as analyzed
type IID fromin own works.
Table Moreover,
2 where experimental
nano-sized ceramicwork matrix is
revealed a relationship between the size of metal particles and the size of the spinel. It was
combined with micro-sized Ti particles and nanoparticles of Zr-Ti-O phase and ZrTiO2.
found that the contribution of spinel volume is even eight times higher than the volume
of the metal particles [58,59]. In such a spinel volume in microstructures, its influence on
properties can be significant.

Figure 6.
Figure 6. SEM
SEMimages
imagesofofceramic–metal
ceramic–metal composites:
composites: (A) (A)
Al2 O
Al3 -Ni composite, spinel phase NiAl O4 2O4
2O3-Ni composite, spinel phase2NiAl
(light grey)—in red circle are the Ni particles pulled out from
(light grey)—in red circle are the Ni particles pulled out from the matrix the matrix visible;
visible; (B)
(B) Al
Al22O
O33-Fe
-Fe com-
composite, voids after Fe particles have been pulled out, and spinel
posite, voids after Fe particles have been pulled out, and spinel FeAl2O24 around FeAl O 4 around the void is
the void is visible;
visible;
(C) Al2O(C) Alcomposite,
3-Ni 2 O3 -Ni composite, spinelNiAl
spinel phase phase2ONiAl 2 O4grey)
4 (light (lightlocated
grey) located
aroundaround
the Nithe Ni particles;
particles; (D) ZrO2-
(D) ZrO2 -Ti composite, Ti particle (black) and Ti oxides (dark grey) around the particles as well as at
ceramic grain boundaries. Source: results obtained under supervision of K. Konopka.

The spinel is active in crack propagation. Cracks are mostly deflected by the spinel
phase [6,56,57,60]. In cases where all metal is transferred to the spinel phase, the composites
consist of two phases, i.e., ceramics and spinel. The microstructure of this composite can
be considered as a typical classical two-phase composite. On the contrary, when both
J. Compos. Sci. 2022, 6, 178 10 of 18

spinel and metal are in the composite microstructure, various spinel locations and its
thickness can be noticed. As presented in Figure 6C, in composite Al2 O3 -Ni, the spinel
phase NiAl2 O4 consists of fine grains surrounding the metal particles and does not have a
regular shape and thickness. Such a microstructure can be classified as a complex ternary
microstructure of composite where the ceramic is a matrix, and the metal and spinel phase
are reinforcements. Such a complex microstructure depends on the shape and distribution
of the spinel, and there are no geometrical schemas of it in Table 2.
In the same group as the above-mentioned group of CMCs are composites in which
various oxides of metals are formed. Their location can create the complex microstructures.
Very fine oxide particles can be located at grain boundaries of the ceramic matrix as well as
at ceramic/metal interfaces and also inside the grains and interlocked by ceramic grains
(Figure 6D). These fine particles of oxides can very effectively stop and redirect the crack
propagation. Moreover, because of their high hardness, the effect of hardening can be
noticed. Our own investigations of composites ZrO2 -Ni and ZrO2 -Ti, in which very fine
oxides particles were identified, confirm this effect [53,54,57]. In particular, in the ZrO2 -Ti
system, very fine (100 nm) phases, Zr-Ti-O and precipitation of titanium oxides ZrTiO2 were
located in the ceramic matrix [49]. This composite geometrical schema of a microstructure
can be considered as type IID from Table 2 where nano-sized ceramic matrix is combined
with micro-sized Ti particles and nanoparticles of Zr-Ti-O phase and ZrTiO2 .
Another example of CMCs with complex microstructures are composites which are
fabricated by consolidation of composite powders. For example, reactive milling of initial
substrates NiO and Al leads to the production of composite powder NiAl-Al2 O3 , and
then after consolidation of it, the NiAl-Al2 O3 bulk composites are obtained [61]. Complex
microstructures of such composites depend on the size, shape and distribution of the
new products.
Our own research also concentrated on such composites. The following concept of
them has been developed. Substrates as two metals in the form of powder are selected in
such a way that during proper processing they will create new a compound, intermetallic
material. From these two selected metals and the added ceramic powders, a composite
powder is prepared (called pre-composite powder). This pre-composite powder consists of
intermetallic material and ceramics. In the next step of the process, pre-composite powder
is mixed with ceramic powder and consolidated to obtain the final bulk ceramic matrix
composite. As an advantage of this concept, uniform distribution of constituencies in pre-
composite powder and, moreover, being kept in bulk composites formed by consolidation
of pre-composite and ceramic powders should be underlined. Finally, the microstructures of
composites have ceramic matrix and reinforcement composed of two phases, intermetallic
and ceramics. Such composites belong to novel bulk ceramic matrix composites with
intermetallic phase, complex structures and improved mechanical properties. However, in
the literature, it is mostly results of intermetallic–ceramic composites that are presented, or
ceramic–intermetallic composites fabricated from initial ceramic and intermetallic powders.
The innovative method of composites fabrication using the pre-composite powder
consisting of the intermetallic compound comes from the fact that intermetallic material is
also regarded as efficient reinforcement of composites, for example, composites of Al2 O3 -
TiAl [10]. The intermetallic particles can retard the crack propagation and deflect the crack
path, and therefore, the stress is released and the fracture energy is increased. Moreover,
the intermetallic phase could also contribute to the hardness of the composite due to its
high hardness [11]. NiAl is a potential material for use in high temperature applications.
The melting point of NiAl is as high as 1640 ◦ C; furthermore, the oxidation and corrosion
resistance of NiAl are superior among intermetallic materials. The elastic modulus of NiAl
is lower than that of Al2 O3 (188 GPa vs. 380 GPa); however, the toughness of NiAl is
higher than that of Al2 O3 [16]. Because of that, various materials are added to NiAl to
make a composite with improvement in fracture toughness. Among of them are NiAl-
Al2 O3 composite [61]. Moreover, the chemical inertness of alumina may not be degraded
 J. Compos. Sci. 2022, 6, 178 11 of 18

significantly as NiAl is added. Both materials NiAl and Al2 O3 have low density. These
features make NiAl an excellent partner to work together with Al2 O3 .
Composites with a ceramic matrix (Al2 O3 ) and intermetallic phase (NiAl) fabricated
from pre-composite powder have been intensively investigated by the group of K. Konopka
within the frame of a project within the Excellence Initiative: Research University (IDUB)
program funded by Warsaw University of Technology. In elaborated composites, complex
structures and positive results of intermetallic material distributed in a ceramic matrix on
mechanical properties are expected. In particular, because of a lower value of NiAl elastic
modulus than for Al2 O3 matrix, the bridging effect can appear as well as deflection of
. Compos. Sci. 2022, 6, x FOR PEER REVIEW 12
the crack path by NiAl. Our own preliminary results are presented in [62]. A schematic
diagram of the technological steps in the fabrication of a new type of hybrid composite is
presented in Figure 7.

Figure 7. Schematic diagram of technological steps of bulk composite fabrication.

Figure 7. Schematic diagram of technological steps of bulk composite fabrication.
Geometrical schemas of composites representing the proposed concept include some
possible variants of selection of metals, ceramics as well as size of their powders. These
Geometrical schemas of composites representing the proposed concept include
variants of pre-composite powders are presented in Table 3. The schemas of predicted
possible variantsofof
microstructures selection
composites of metals,
obtained ceramics as
by consolidation well as size powder
of pre-composite of their(repre-
powders. T
variants ofTable
sented in pre-composite powders
3) with ceramic powder areareproposed
presented in Table
in Table 4. 3. The schemas of pred
The proposed
microstructures of concept could obtained
composites create the bulk ceramic matrix composites
by consolidation with inter-
of pre-composite powder
metallic phase. It is expected that in areas composed of
resented in Table 3) with ceramic powder are proposed in Table 4.pre-composite powder, the in-
termetallic phase will make continuous interlocking skeletons and effectively take part
in crack propagation. The crack propagation should be stopped and should not transfer
to the neighboring grains. Such behavior should be observed in all types of composites
composed of pre-composite powders (Table 4 type IIIA, IIIB, IIIC, IIID). Additionally, the
nanoparticles of ceramics in pre-compo 1 powder (Table 3) and finally in composites types
IIIA and III B (Table 4) should also take part in the process of crack path propagation, espe-
cially by stopping or redirecting the cracks. Ceramic–intermetallic composites with such
microstructures seem to be very promising for possible application as high temperature
structural materials in the energy industry, aerospace or as a wear-resistant material.
J. Compos. Sci. 2022, 6, 178 12 of 18

J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 13 of 20

J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 13 of 20
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 13 of 20
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW 13 of 20
TableREVIEW
J. Compos. Sci. 2022, 6, x FOR PEER 3. Types of microstructures of pre-composite powders fabricated by consolidation of powders,
13 of 20
one ceramic
J. Compos. Sci. 2022,and two
6, x FOR PEERmetals,
REVIEW with various variants of ceramics and metal powder size and13their of 20
Table 3. Types of microstructures of pre‐composite powders fabricated by consolidation of pow‐
geometrical
Table schemas.
3. Types Table
of 3. Types of microstructures
microstructures of of pre‐composite
pre‐composite powders
powders fabricated by
fabricated by consolidation
consolidation of pow‐
of pow‐
ders, one ceramic ders, and two metals,
one ceramic and two with various
metals, variants
with various of ceramics
variants ceramics and
offabricated andby metalpowder
metal powder size size
and and
Tableone
ders, 3. Types
ceramic of and
microstructures
two metals, of pre‐composite
with various powders
variants of ceramics and consolidation
metal powder of pow‐
size and
their
Table geometrical
3. Types schemas.
their geometrical
of Table schemas.
microstructures
3. Types of pre‐composite
of microstructures powders
of pre‐composite fabricated
powders fabricated by consolidation
Schema
by metal of
consolidation of pow‐
of pow‐
ders, geometrical
their one ceramic
Matrix and two
schemas. metals, with various
Reinforcement variants of ceramics and powder size and
ders, one ceramic ders,
and one
twoceramic and
metals, two metals,
with variouswith various
variantsvariants of ceramicsand
of ceramics and metal
metal powder
powdersize and
size and
their geometrical schemas. Microstructure
Schema
Schema of of
Typetheir geometrical Matrix their geometricalReinforcement
schemas.
Matrix Ceramics
Reinforcement
schemas.
Metal Metal Schema of
Microstructure
Type Matrix
Ceramics ReinforcementMetal Metal
Microstructure
Schema
Schema
C1 + M1 ofx of
M2y
Type Matrix
C1 Reinforcement
M1 Microstructure
Type Matrix
Ceramics C1
Reinforcement
Metal M1 MetalM2
M2
C1 + M1xM2
Schema ofy
Microstructure
Microstructure
Matrix
Type
Ceramics Reinforcement
Metal Metalμm C1 + M1xM2y
Type C1 Ceramics
M1 μmMetal M2 Metal Microstructure
C1
C1 ++M1
M1 xM2
xM2
Type Ceramics
C1 C1 Metal
M1 M1
µm
Metalµm
M2 M2
y y
Ceramics C1 + M1xM2y
C1 nano Metal
nano μm
M1 μm Metal
μm
M2 μm C1 + M1xM2y
Pre-comp
Pre‐comp
C1 1 1
(white)M1
μm M1xM2y μm
M2
(white) μm M1x M2y μm
nano 1 nano (grey)
(white)μm μm
Pre‐comp M1xM2y
Pre‐comp 1 nano M1xM2y (grey)
(grey)
Pre‐comp 1 (white)
nano M1xM2y
Pre‐comp 1 (white) (grey)
M1xM2y μm μm
nano (grey)
Pre‐comp 1 (white) M1xM2y μm μm
(white) μm (grey) µm µm
Pre‐comp2 µm (grey)
μm μm M1xM2y
Pre-comp2 (white)
μm
Pre‐comp2 (white) μm μm(grey)
M1xM2y
(white) μm μm (grey)
M1x M2y
μm μm μm
Pre‐comp2 μm (grey) M1xM2y
Pre‐comp2 (white)
μm Table 4. Types of microstructures M1 xM2y
of ceramic–metal composites fabricated by consolidation of pow‐
Pre‐comp2 (white) (grey)
M1 M2y with various
μm ders,Table 4. Types and
one ceramic of microstructures
pre‐composite xceramic–metal
ofpowder
(grey) composites fabricated
variants by consolidation
of ceramics powder of pow‐
size and
Pre‐comp2 (white) ders, one
geometrical M1xM2
ceramic and pre‐composite
schemas. y
powder with various variants of ceramics powder size and
(white)
Table 4. Types of microstructures
geometrical of ceramic–metal
schemas.
(grey)
composites fabricated by consolidation of pow-
Matrix
(grey)
Reinforcement Schema of Microstructure
ders, one ceramic and pre-composite
Matrix powder with various variants of ceramics
Reinforcement Schema ofpowder size and
Microstructure
Type Table 4. Types Ceramics
of microstructures of ceramic–metal composites fabricated by consolidation of pow‐
geometrical
Type schemas. Ceramics Composite Powder C1 + Pre‐Comp Powder
Table 4. Types
ders, one of microstructures
C1
ceramic and of ceramic–metal
pre‐composite Composite
powder with composites
various fabricated
Powder variantsC1of by consolidation
+ Pre‐Comp
ceramics Powder
powder of pow‐
size and
Tableone
4. Types C1
of microstructures of ceramic–metal
ders,
geometricalceramic and pre‐composite
schemas. powder with composites fabricated
various variants by consolidation
of ceramics powder size of pow‐
and
Table 4. Types
ders, one of microstructures
ceramic of ceramic–metal
and pre‐composite powder withcomposites fabricated
Schema
various variants by
of consolidation
of ceramics powder sizeof pow‐
and
geometrical Matrix
schemas. Reinforcement
Pre‐comp1
ders, one
geometricalceramic and
schemas.
μm pre‐composite powder with
Pre‐comp1 various Microstructure
variants of ceramics powder size and
III A IIITypeMatrix μm Reinforcement
μmμm Schema of Microstructure
A geometrical
Matrix schemas.
(white)
Ceramics Reinforcement Schema of Microstructure
Type Ceramics (white) (grey + white dots)
Matrix Composite
Reinforcement
(grey Powder
+ white dots) C1 + Pre-Comp
Schema Powder
of Microstructure
Type Ceramics C1 Composite Powder C1 + Pre‐Comp Powder
Matrix
C1 Reinforcement
Composite Powder Schema of Microstructure
C1 + Pre‐Comp Powder
Type Ceramics
C1
Type Ceramics Composite Powder C1 + Pre‐Comp Powder
C1 Composite Powder C1 + Pre‐Comp Powder
C1 Pre‐comp1
Pre‐comp1
nanonano
III B III B Pre‐comp1
μmμm
Pre-comp1
μm (white)
(white)
µm Pre‐comp1 (grey
(grey + whitedots)
+ white dots)
III A III A μm μm µm
Pre‐comp1
III A (white) (white) μm
μm (grey
Pre‐comp1
(grey white dots) dots)
+ white
III A (white)
μm μm ++ white
(grey dots)
III A (white) μm
(white) (grey + Pre‐comp2
white dots)
Pre‐comp2
IIIC μm μm (grey + μm
white
μm dots)
IIIC (white)
(white) (grey + white dots)
(grey + white dots)
Pre‐comp1
nano Pre‐comp1
Pre-comp1
III B nano nano μm
Pre‐comp1
III B III B (white)
nano μm µm
Pre‐comp1
III B (white) (white) (grey
μm + white dots)
Pre‐comp2
nano nano
(grey + (grey + dots)
Pre‐comp2
white white dots)
III B III D (white) nano(white) μm μm
III D (white) (grey + μm
white
(grey +dots)
white dots)
(white) (grey + (grey
white dots)dots)
+ white
Pre‐comp2
μm The proposed Pre‐comp2
concept could create the bulk ceramic matrix composites with inter‐
IIIC μm metallic
The proposed μm
Pre‐comp2
phase. Itconcept
is expected thatcreate
could in areas
thecomposed of pre‐composite
bulk ceramic powder,with
matrix composites the inter‐
inter‐
IIIC (white) μm Pre-comp2
μm µmmetallic phase Pre‐comp2
(grey
It iswill make+continuous
white dots)
interlocking skeletons and effectively takethe
part in
IIIC IIIC (white)
μm metallic phase. expected
μm that
µm in areas composed of pre‐composite powder, inter‐
IIIC (white) (white)
crackphase
metallic propagation. (grey
μm
will make + white
The continuous
crack dots)
propagation should skeletons
interlocking be stoppedand
andeffectively
should nottake
transfer
parttoin
(grey (grey + white dots)
+ propagation
white dots)should be stopped and should not transfer to
(white) crack propagation. The crack
(grey + white dots)

Pre‐comp2
nano Pre‐comp2
III D nano μm
Pre‐comp2
III D (white)
nano μm
(white) Pre‐comp2
(grey + Pre-comp2
white dots)
III D nano nano μm
(grey + µm
white dots)
III D III D (white) μm
(white) (white) (grey + white dots)
(grey + (grey
white+ dots)
white dots)
The proposed concept could create the bulk ceramic matrix composites with inter‐
The
metallic proposed
phase. It is concept
expectedcould create
that in areasthe bulk ceramic
composed matrix composites
of pre‐composite powder, with
the inter‐
inter‐
The
metallic proposed
phase. concept
It is concept
expected could create
that in areas the bulk
composed ceramic matrix composites
of pre‐composite powder, with inter‐
thepart
inter‐
The
metallic
metallic proposed
phase
phase. will
It is make
expectedcould
that create
continuous
in areas the bulk
interlocking
composed ceramic
of matrix
skeletons and composites
effectively
pre‐composite powder, with
takethe inter‐
in
inter‐
metallic
metallic
crack phase will
phase. It
propagation. is make
The continuous
expected
crack that in interlocking
areas
propagation composed
should skeletons
be of and effectively
pre‐composite
stopped and powder,
should take
not thepart in
inter‐
transfer to
metallic
crack phase will make
propagation. continuous interlocking skeletons and
andeffectively take part in
metallic phase will The
crack propagation. make
The
crack
crack
propagation
continuous should be
interlocking
propagation should be
stoppedand
skeletons should nottake
stopped andeffectively
transfer
part to
should not transfer in
to
crack propagation. The crack propagation should be stopped and should not transfer to
 posed of pre-composite powders (Table 4 type IIIA, IIIB, IIIC, IIID). Additionally, the na-
noparticles of ceramics in pre-compo 1 powder (Table 3) and finally in composites types
IIIA and III B (Table 4) should also take part in the process of crack path propagation,
especially by stopping or redirecting the cracks. Ceramic–intermetallic composites with
such microstructures seem to be very promising for possible application as high temper-
J. Compos. Sci. 2022, 6, 178 13 of 18
ature structural materials in the energy industry, aerospace or as a wear-resistant material.

4. Effect of CMCs Structure on Properties

4. Effect of CMCs Structure on Properties
The most important aim of introducing reinforcement into a ceramic matrix is im-
provingThethe
most important
fracture aim ofofintroducing
toughness reinforcement
new materials compare tointo
the aceramics.
ceramic matrix is im-
The mecha-
proving the fracture toughness of new materials compare to the ceramics.
nisms of improving the fracture toughness depend on the ceramic–metal system and com- The mech-
anisms
posite of improving the
microstructures. Thefracture
bridgingtoughness depend
and deflection on thebyceramic–metal
of cracks system
the metal particles and
as the
composite microstructures. The bridging and deflection of cracks by the metal
effective mechanisms of crack energy dissipation and increasing fracture toughness are particles
as the
well effective
known [5–7].mechanisms
The strengthofofcrack energy between
the interface dissipation and increasing
ceramics and metalfracture tough-
is responsible
for the operation of these particular mechanisms of fracture toughness improvementmetal
ness are well known [5–7]. The strength of the interface between ceramics and [5–
is responsible
7] (Figure 8). for the operation of these particular mechanisms of fracture toughness
improvement [5–7] (Figure 8).

Diagramshowing
Figure8.8.Diagram
Figure showingrelationship
relationshipbetween
betweenceramics/metal
ceramics/metalinterface
interfacestrength
strengthand
andmechanism
mechanism
ofoffracture
fracturetoughness
toughnessimprovement.
improvement.

Forweak
For weakbonding
bondingbetween
betweenceramics
ceramicsand
andmetal
metalparticles
particlescrack
crackpropagation
propagationalongalongthe
the
interface, deflection of the crack path is dominated [5–7]. Moreover, the
interface, deflection of the crack path is dominated [5–7]. Moreover, the metal particles metal particles
arebeing
are beingpulled
pulledout
outfrom
fromthetheceramic
ceramicmatrix.
matrix.Strong
Stronginterface
interfacebonding
bondingbetween
betweenceramics
ceramics
and metal particles results in a bridging mechanism. It is the most effective
and metal particles results in a bridging mechanism. It is the most effective mechanism mechanism
becauseititinvolves
because involvesthe
theplastic
plasticdeformation
deformationofofmetal
metalparticles
particles[5,7].
[5,7].There
Therearearealso
alsoother
other
mechanismswhich
mechanisms whichcancanbebe active
active in ceramics
in ceramics as well
as well as inasceramic
in ceramic
matrixmatrix composites,
composites, i.e.,
transformation toughening, micro-crack toughening, bridging by matrix grains ororcrack
i.e., transformation toughening, micro-crack toughening, bridging by matrix grains crack
fieldvoids
field voidsformation
formation[63].
[63].InIncomposites
compositeswith
withZrO
ZrO2 2matrix,
matrix,the themartensitic
martensitictransformation
transformation
of tetragonal t-ZrO into monoclinic m-ZrO is possible [6,64]. The metal
of tetragonal t-ZrO2 2into monoclinic m-ZrO2 2is possible [6,64]. The metal particles such particles suchasas
Ti can influence the martensitic transformation, and in this way, they can
Ti can influence the martensitic transformation, and in this way, they can exert an influ-exert an influence
on strength and fracture toughness of composite material [65,66].
ence on strength and fracture toughness of composite material [65,66].
Nanoparticles of metal and their influence on the properties of ceramic matrix compos-
Nanoparticles of metal and their influence on the properties of ceramic matrix com-
ites are also the subject of research [5,6,9]. In the fabrication process, the nanopowders of
posites are also the subject of research [5,6,9]. In the fabrication process, the nanopowders
metal are mixed with micro- or nano-ceramic powder. As a result, composite nanoparticles
of metal are mixed with micro- or nano-ceramic powder. As a result, composite nanopar-
of metal are situated as separated particles surrounded by ceramic grains, or at the ceramic
ticles of metal are situated as separated particles surrounded by ceramic grains, or at the
grains boundaries as well as in triple points. Nanocomposites represent hard materials
but with improving fracture toughness, which is an effect of nanoparticles of metal, which
very effectively stopped the crack propagation [52]. For nanoparticles situated along the
grain boundaries, their tendency to change the intergranular fracture to transgranular and
toughen the composites were noticed [15].
All of the mechanisms for crack energy dissipation by reinforcement phase in CMCs
are active in hybrid composites. The multiscale effect of micro- and nanoparticles of
reinforcement on the microstructure and properties of advanced hybrid composites has not
been thoroughly studied. However, the synergistic effect of different mechanisms of crack
energy dissipation is announced [9,50]. Niihara et al. [67] have shown that the hybridization
J. Compos. Sci. 2022, 6, 178 14 of 18

of microcomposites and nanocomposites leads to improvements in strength and toughness.

For example, in multiphase composites, Al2 O3 -ZrO2 -CeO2 with the addition of Ni, or
TiO2 led to an increase in the fracture toughness being obtained [50]. In the work of
Kim et al. [68], a fabricated composite consisting of 40 vol.% of ZrO2 , 30 vol. % spinel and
30 vol.%Al2 O3 exhibited a higher strength compared with the strengths of the constituent
phases. The bend strength of composite sintered at 1550 ◦ C was equal to 658 MPa [68].
The increase in fracture toughness while keeping the high hardness is also observed
in own investigation of composites with spinel phase [57,59].
In composites with an intermetallic phase, the intermetallic particles can retard the
crack propagation and deflect the crack path; therefore, the stress is released and the
fracture energy is increased. Moreover, the intermetallic phase could also contribute to the
hardness of composite, due to the high hardness of the former [12].
However, the state of knowledge concerning hybrid composites of ternary systems and
multiphase systems is inconsiderable. It is because of this fact that in hybrid composites,
as a consequence of their complex structure obtained by the intermixing of different
phases with various size, shape and distribution, describing the relationships between the
structures and properties is difficult. In particular, it should be expected that cracks reaching
the areas of complex phases, due to simultaneous activation of various mechanisms as
J. Compos. Sci. 2022, 6, x FOR PEER REVIEW
redirection, deflection, and pulling out, will be effectively stopped and will not 16 of 20
coming
out, as presented in Figure 9A. Such an effect is predicted in composites composed of
compaction of pre-composite powder represented by all geometry models (Table 4).

Figure9.9.SEM
Figure SEMimages
imagesofofZrO
ZrO2-Ti
2 -Ticomposite
compositeobtained
obtainedbybyslip
slipcasting
castingmethod:
method:(A)(A)crack
crackpropagation
propagation
in area of complex distribution of Ti particles mixed with ZrO particles in ZrO matrix;
in area of complex distribution of Ti particles mixed with ZrO2 particles in ZrO2 matrix; (B,C)
2 2 (B,C)cracks
cracks
passesthrough
passes through the
the Ti
Ti particle, bridging
bridging by
by Ti
Tiparticles.
particles.Source:
Source:results
resultsobtained
obtainedunder
undersupervision
supervisionof
ofK.K.Konopka.
Konopka.

In hybrid composites, the bigger particles, separately located in the ceramic matrix,
5. Summary
will also contribute to the interaction with the propagating crack. The crack propagation
This paper presents some examples of ceramic matrix composites (CMCs) reinforced
through the metal particle or new phases and crack bridging are expected, as presented
by metal or intermetallic phases fabricated by powders consolidation without the liquid
phase (melted metal). Composites with complex structure which are advanced group of
CMCs, also called hybrid composites, are described in contrast to conventional compo-
sites with a ceramic matrix. In advanced CMCs, their complex structures give us the pos-
sibility to achieve the improvement of properties, which is not available in conventional
J. Compos. Sci. 2022, 6, 178 15 of 18

in Figure 9B,C. For example, for composite ZrO2 with 10 vol.% of Ti, a positive effect of
formed Ti-Zr-O phases for mechanical properties of composite was noticed. Hardness was
equal to 11.2 GPa and bending stress 170 MPa. On the contrary, for the reference sample
ZrO2 , hardness was equal to 12.5 GPa and bending stress 220 MPa. The fracture toughness,
measured by Vickers indentation method, for composite was almost two times larger than
for pure ceramics [55,69].
In composites which were prepared from pre-composite powder according to the
concept presented in paper, the high hardness was achieved. First, pre-composite powder
was prepared by mechanical alloying of powder mixture Ni-50 at.% Al with contribution
of 10 and 20 wt.% of nanometric Al2 O3 powder. Then, Puls Plasma Sintering was applied
as the consolidation method, and as a result, composites with the nanocrystalline NiAl
matrix and fine inclusions of Al2 O3 were obtained. These composites had a hardness equal
to 7.2 GPa for 10 wt.% Al2 O3 and 8.4 GPa for 20 wt.% Al2 O3 [62].
Additionally, using pre-composite powder as an initial powder mixed with Al2 O3 pow-
der, and by slip casting produced bulk materials which gave the composites
(Al2 O3 —(NiAl + Al2 O3 )) with complex structures high density and favorable mechan-
ical properties. In samples using initial pre-compo-powder (2.5 vol.% of (NiAl + Al2 O3 )),
the fracture toughness was equal to 6.2 MPa·m0.5 . For samples using initial pre-compo-
powder (5 vol.% of (NiAl + Al2 O3 )), the fracture toughness was equal to 6.19 MPa·m0.5 . In
addition, the fracture toughness value for pure Al2 O3 ceramics was 5.18 MPa·m 0.5 [70].

5. Summary
This paper presents some examples of ceramic matrix composites (CMCs) reinforced
by metal or intermetallic phases fabricated by powders consolidation without the liquid
phase (melted metal). Composites with complex structure which are advanced group of
CMCs, also called hybrid composites, are described in contrast to conventional composites
with a ceramic matrix. In advanced CMCs, their complex structures give us the possibility
to achieve the improvement of properties, which is not available in conventional materials.
It is an effect of the complex microstructure made by various phases and by micro and
nanoparticles of reinforcement. Some potential types of micro-nano hybrid structure
together with their schemas of microstructures were presented. Proposed schemas of
microstructures of ceramic matrix composites are based only on possible combinations of
initial size of ceramic and metal powders; however, in the literature, there are not so many
works which presented the model of predicted location of ceramic, metallic or intermetallic
phases in CMCs fabricated by the consolidation of powders. Rodriguez-Suarez, Bartolome
and Moya [9] presented geometrical model established for nanoparticles. Presented in this
paper are schemas of the microstructures of advanced CMCs which can be useful in the
process of composites tailoring and prediction of their microstructures and consequently
their properties. The selected examples of real CMCs with a corresponding schema of
microstructure were described.
A new concept of advanced ceramic–intermetallic composite fabricated by consoli-
dation of pre-composite powder mixed with ceramic powder was also presented. This
concept is based on the selection of substrates, two metals in the form of powder which
will made a new compound intermetallic material, during processing. Additionally, during
milling, the ceramic powders are added to the metal powders to obtain the pre-composite
powder consisting of intermetallic material and ceramics. In the next step, consolida-
tion of pre-composite powder with ceramic powder allows us to create composites with
complex microstructures.

Author Contributions: Conceptualization, K.K.; methodology, K.K.; software, K.K.; validation, K.K.;
formal analysis, K.K.; investigation, K.K.; resources, data curation, K.K.; writing—original draft
preparation, K.K.; writing—review and editing, K.K.; visualization, K.K.; supervision, K.K.; project
administration, K.K.; funding acquisition, K.K. All authors have read and agreed to the published
version of the manuscript.
J. Compos. Sci. 2022, 6, 178 16 of 18

Funding: This paper is completed partially within the frame of work realized as subvention work of
the Faculty of Materials Science and Engineering Warsaw University of Technology. The research
concerning the ceramic–intermetallic composites made with using pre-composite powder was funded
by POB Technologie Materiałowe of Warsaw University of Technology within the Excellence Initiative:
Research University (IDUB) programme.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data sharing not applicable.
Acknowledgments: This paper is completed partially within the frame of work realized as subven-
tion work of the Faculty of Materials Science and Engineering Warsaw University of Technology. The
research concerning the ceramic–intermetallic composites made with using pre-composite powder
was funded by POB Technologie Materiałowe of Warsaw University of Technology within the Excel-
lence Initiative: Research University (IDUB) program. Manager: Katarzyna Konopka. The author is
pleased to have this opportunity to express sincere gratitude to all the students and co-workers who
contributed to the research under the author’s supervision.
Conflicts of Interest: The author declares no conflict of interest.

References
1. Donald, I.W.; McMillan, P.W. Ceramic matrix composites. J. Mater. Sci. 1976, 11, 949–972. [CrossRef]
2. Jones, S.A.; Burlitch, J.M.; Üstündag, E.; Yoo, J.; Zehnder, A.T. Ceramic–matrix composites—advanced high temperature materials.
In Materials Research Society Symposium Proceedings; Lowden, R.A., Ferber, M.K., Hellman, J.R., Chawla, K.K., DiPietro, S.G., Eds.;
Materials Research Society: Pittsburgh, PA, USA, 1995; Volume 365, pp. 53–58.
3. Eckold, G.C. Design and Manufacture of Composite Structures, 1st ed.; Woodhead Publishing: Sawston, UK, 1994; pp. 1–400.
4. Sternitzke, M. Structural ceramic nanocomposites. J. Eur. Ceram. Soc. 1997, 17, 1061–1082. [CrossRef]
5. Yeomans, J.A. Ductile particle ceramic matrix composites-scientific curiosities or engineering materials? J. Eur. Ceram. Soc. 2008,
28, 1543–1550. [CrossRef]
6. Moya, J.S.; Esteban, S.L.; Pecharroman, C. The challenge of ceramic/metal microcomposities and nanocomposities. Prog. Mater.
Sci. 2007, 52, 1017–1090. [CrossRef]
7. Sun, X.; Yeomans, Y. Optimization of a ductile particle-toughened ceramic. J. Am. Ceram. Soc. 1996, 79, 2705–2717. [CrossRef]
8. Ashby, M.F.; Brecht, Y.J.M. Designing hybrid materials. Acta Mater. 2003, 51, 5801–5809. [CrossRef]
9. Rodrigues-Suarez, T.; Bartolome, J.F.; Moya, J.S. Mechanical and tribological properties of ceramic/metal composites: A revive of
phenomena spanning from the nanometer to the micrometer length scale. J. Eur. Ceram. Soc. 2012, 32, 3887–3898. [CrossRef]
10. Xiang, L.; Wang, F.; Zhu, J.; Wang, X. Mechanical properties and microstructure of Al2 O3 /TiAl in situ composites doped with
Cr2 O3 . Mater. Sci. Eng. A 2011, 528, 3337–3341. [CrossRef]
11. Tuan, W.H.; Pai, Y.P. Mechanical properties of Al2 O3 -NiAl composites. J. Am. Ceram. Soc. 1999, 82, 1624–1626. [CrossRef]
12. Lu, X.; Li, J.; Chen, X.; Rau, C.; Wang, Y.; Liu, B.; Liu, Y.; Rashad, M.; Pan, F. Grinding mechanism and mechanical properties of
the in-situ synthesized Al2 O3 /TiAl composites. Ceram. Int. 2019, 45, 12113–12121. [CrossRef]
13. Rodriguez-Suarez, T.; Bartolomé, J.F.; Smirnov, A.; Lopez-Esteban, S.; Díaz, L.A.; Torrecillas, R.; Moya, J. Electroconductive
alumina–TiC–Ni nanocomposites obtained by spark plasma sintering. Ceram. Int. 2011, 37, 1631–1636. [CrossRef]
14. Sawaguchi, A.; Tool, K.; Nihara, K. Mechanical and electrical properties of nano-composites. J. Amer. Ceram. Soc. 1991, 74,
1142–1144. [CrossRef]
15. Tan, H.; Yang, W. Toughening mechanisms of nano-composite ceramics. Mech. Mater. 1998, 30, 111–123. [CrossRef]
16. Tuan, W.H. Toughening alumina with nickel aluminide. J. Eur. Ceram. Soc. 2000, 20, 895–899. [CrossRef]
17. Isobe, T.; Daimon, K.; Sato, T.; Matsubara, T.; Hikichi, Y.; Ota, T. Spark plasma sintering technique for reaction sintering of
Al2 O3 /Ni nanocomposite and its mechanical properties. Ceram. Int. 2008, 34, 213–217. [CrossRef]
18. Rodriguez-Suarez, T.; Bartolome, J.F.; Smirnov, A.; Lopez-Esteban, S.; Torrecillas, R.; Moya, J.S. Sliding wear behavior of
alumina/nickel nanocomposites processed by a conventional sintering route. J. Eur. Ceram. Soc. 2011, 31, 1389–1395. [CrossRef]
19. Aharon, O.; Bar-Ziv, S.; Cohen-Hyams, T.; Kaplan, W.D. Residual stresses and magnetic properties of alumina-nickel nanocom-
posites. Scr. Mater. 2004, 50, 1209–1213. [CrossRef]
20. Chou, S.-N.; Lu, H.-W.; Lii, D.-F.; Huang, J.-L. Processing and physical properties of Al2 O3 /alumina alloy composites. Ceram. Int.
2009, 35, 7–12. [CrossRef]
21. Imbeni, V.; Hutchings, I.M.; Breslin, M.C. Abrasive wear behavior of Al2 O3 -Al co-continuous composite. Wear 1999, 233–235,
462–467. [CrossRef]
22. Qi, Y.; Zhang, Y.-S.; Hu, L.-T. High temperatures self-lubricated properties of Al2 O3 /Mo laminated composites. Wear 2012,
280–281, 1–4. [CrossRef]
J. Compos. Sci. 2022, 6, 178 17 of 18

23. Moya, J.S.; Diaz, M.; Gutierez-Gonzalez, C.F.; Diaz, L.A.; Torrecillas, R.; Bartolome, J.F. Mullite-refractory metal (Mo, Nb)
composites. J. Eur. Ceram. Soc. 2008, 28, 479–491. [CrossRef]
24. Augusto, T.; Restivo, G.; Beccari, R.F.; Padilha, W.R.; Durazzo, M.; Telles, V.B.; Coleti, J.; Yamagata, C.; Silva, A.C.; Suzuki, E.; et al.
Micrograded ceramic-metal composites. J. Eur. Ceram. Soc. 2019, 39, 3484–3490. [CrossRef]
25. Zhou, W.; Ai, S.; Chen, M.; Zhang, R.; He, R.; Pei, Y.; Fang, D. Preparation and thermodynamic analysis of the porous
ZrO2 /(ZrO2 +Ni) functionally graded bolted joint. Compos. Part B 2015, 82, 13–22. [CrossRef]
26. Ahlhelm, M.; Günther, P.; Schwarzer, E.; Günther, A.; Slawik, T.; Moritz, T.; Michaelis, A. Innovative and novel manufacturing
methods of ceramics and metal-ceramic composites for biomedical applications. J. Eur. Ceram. Soc. 2016, 36, 2883–2888. [CrossRef]
27. Smirnov, A.; Bartolome, J.F. Mechanical properties and fatigue life of ZrO2 -Ta composites prepared by hot-pressing. J. Eur. Ceram.
Soc. 2012, 32, 3899–3904. [CrossRef]
28. Zhu, S.L.; Wang, X.M.; Xie, G.Q.; Qiu, F.X.; Yoshimura, M.; Inoue, A. Formation of Ti-based bulk glassy/alloy/hydroksyapatite
composite. Scr. Mater. 2008, 58, 287–290. [CrossRef]
29. Chang, Q.; Chen, D.L.; Ru, H.Q.; Yue, X.Y.; Yu, L.; Zhang, C.P. Toughening mechanisms in iron-containing hydroksyapatite
titanium composites. Biomaterials 2010, 31, 1493–1501. [CrossRef]
30. Kawasaki, A.; Watnabe, R. Concept and P/M fabrication of functionally gradient materials. Ceram. Int. 1997, 23, 73–83. [CrossRef]
31. Suresh, S.; Mortensen, A. Fundamentals of Functionally Graded Materials; Cambridge University Press: Cambridge, UK, 1998.
32. Miyamoto, Y.; Kaysser, W.A.; Rabin, B.H.; Kawasaki, A.; Ford, R.G. Functionally Graded Materials, Design, Processing and Applications;
Kluwer Academic Publishers: Boston, MA, USA, 1999.
33. Kawasaki, A.; Watanabe, R. Effect of gradient microstructure on thermal shock crack extension in metal/ceramic functionally
graded materials. In Proceedings of the 4th International Symposium on Functionally Graded Materials, Tsukuba, Japan, 21–24
October 1996.
34. Ogawa, T.; Watanabe, Y.; Sato, H.; Kim, I.S.; Fukui, Y. Theoretical study on fabrication of functionally graded material with
density gradient by a centrifugal solid-particle method. Compos. Part A Appl. 2006, 37, 2194–2200. [CrossRef]
35. Tjong, S.S.; Ma, Z. Microstructural and mechanical characteristics of in situ metal matrix composite. Mater. Sci. Eng. 2000, 29,
49–114. [CrossRef]
36. Szafran, M.; Konopka, K.; Bobryk, E.; Kurzydłowski, K.J. Ceramic matrix composites with gradient concentration of metal
particles. J. Eur. Ceram. Soc. 2007, 27, 651–654. [CrossRef]
37. Mortensen, A.; Suresh, S. Functionally graded metals and metal-ceramic composites: Part I Processing. Inter. Mater. Rev. 1995, 40,
239–265. [CrossRef]
38. Ilschner, B. Structural and compositional gradients: Basic idea, preparation, applications. J. Phys. IV Colloq. 1993, 3, 763–772.
[CrossRef]
39. Nai, S.; Gupta, M.; Lim, C. Synthesis and wear characterization of Al based, free standing functionally graded materials: Effect of
different matrix compositions. Compos. Sci. Technol. 2003, 63, 1895–1909. [CrossRef]
40. Vleugels, J.; Anné, G.; Put, S.; van der Biest, O. Thick plateshaped Al2 O3 /ZrO2 composites with continuous gradient processed
by electrophoretic deposition. Mater. Sci. Forum 2003, 423, 171–176. [CrossRef]
41. Lackner, J.; Waldhauser, W.; Ebner, R.; Major, B.; Schöberl, T. Structural, mechanical and tribological investigations of pulsed laser
deposited titanium nitride coatings. Thin Solid Film. 2004, 453–454, 195–202. [CrossRef]
42. Zygmuntowicz, J.; Miazga, A.; Wiecińska, P.; Kaszuwara, W.; Konopka, K.; Szafran, M. Combined centrifugal slip casting method
used for preparation the Al2 O3 -Ni functionally graded composites. Compos. Part B Eng. 2018, 141, 158–163. [CrossRef]
43. Zygmuntowicz, J.; Wachowski, M.; Piotrkiewicz, P.; Miazga, A.; Konopka, K.; Kaszuwara, W. Characterization ofAl2 O3 /Ni
composites manufactured via CSC technique in magnetic field. Compos. Part B Eng. 2019, 156, 113–120. [CrossRef]
44. Wachowski, M.; Kaszuwara, W.; Miazga, A.; Konopka, K.; Zygmuntowicz, J. The possibility to producing graded Al2 O3 -Mo,
Al2 O3 -Cu, Al2 O3 -W composites using CSC method. Bull. Pol. Acad. Sci. Tech. Sci. PAN 2019, 67, 179–184. [CrossRef]
45. Wachowski, M.; Kosturek, R.; Winkler, H.; Miazga, A.; Łada, P.; Kaszuwara, W.; Konopka, K.; Zygmuntowicz, J. Manufacturing of
ZrO2-Ni graded composites via centrifugal casting in the magnetic field. Bulletin of the Polish Academy of Science. Tech. Sci.
2020, 68, 539–545. [CrossRef]
46. Obadele, B.; Lepule, M.; Andrews, A.; Olubambi, P. Tribocorrosion characteristics of laser deposited Ti-Ni-ZrO2 composite
coatings on AISI316 stainless steel. Tribol. Int. 2014, 78, 160–167. [CrossRef]
47. Mori, M.; Hiei, Y.; Itoh, H.; Tompsett, G.; Sammes, N. Evaluation of Ni and Ti –doped Y2 O3 stabilized ZrO2 cermet as an anode in
high-temperature soild oxide fuel cells. Solid State Ion. 2003, 160, 1–14. [CrossRef]
48. Chakravarty D, Sundararajan G, Microstructure, mechanical properties and machining performance of spark plasma sintered
Al2 O3 -ZrO2 -TiCN nanocomposites. J. Eur. Ceram. Soc. 2013, 33, 2597–2607. [CrossRef]
49. Kunz, C.; Bartolome, J.F.; Gnecco, E.; Muller, F.A. Selective generation of laser-induced periodic surface structures on Al2 O3 -
ZrO2 -Nb composites. Appl. Surf. Sci. 2018, 434, 582–587. [CrossRef]
50. Verma, V.; Manoj Kumar, B.V. Synthesis microstructure and mechanical properties of Al2 O3 /ZrO2 /CeO2 composites with
addition of nickel and titanium processed by conventional sintering. Mater. Today Proc. 2017, 4, 3062–3071. [CrossRef]
51. Zang, B.; Boey, F. The phases and the toughening mechanisms in (Y)ZrO2 -Al2 O3 -(Ti,W)C ceramics system. Mater. Lett. 2000, 43,
197–202. [CrossRef]
52. Konopka, K. Complex micro-nano structure of ceramic-metal composites. Met. Powder Rep. 2020, 75, 106–109. [CrossRef]
J. Compos. Sci. 2022, 6, 178 18 of 18

53. Zygmuntowicz, J.; Falkowski, P.; Miazga, A.; Konopka, K. Fabrication and characterization of ZrO2 /Ni composites. J. Aust.
Ceram. Soc. 2018, 54, 655–662. [CrossRef]
54. Konopka, K.; Łada, P.; Dutkiewicz, J.; Miazga, A.; Maziarz, W. SEM and TEM analysis of composite of ZrO2 -Ti system. Compos.
Interfaces 2018, 25, 1091–1099. [CrossRef]
55. Finally report of project NCN. 2013/11/B/ST8/00309; Ceramic-Metal Composites in ZrO2-Ti System. Principal of the project K.
Konopka. not published.
56. Konopka, K. Alumina composites with metal particles in ceramic matrix. Powder Metall. Met. Ceram. 2015, 54, 374–378. [CrossRef]
57. Zygmuntowicz, J.; Wiecińska, P.; Miazga, A.; Konopka, K. Characterization of composites containing NiAl2 O4 spinel phase from
Al2 O3 /NiO and Al2 O3 /Ni systems. J. Therm. Anal. Calorim. 2016, 125, 1079–1086. [CrossRef]
58. Konopka, K. Novel ceramic-metal composites with metal phase from micro to nanosized. Solid State Phenom. 2005, 101–102,
139–142. [CrossRef]
59. Konopka, K.; Lityńska-Dobrzyńska, L.; Dutkiewicz, J. SEM and TEM characterization of NiAl2 O4 spinel phase in Al2 O3 matrix
Ni composite. Solid State Phenom. 2012, 186, 222–225. [CrossRef]
60. Liberthal, M.; Kaplan, W.D. Processing and properties of Al2 O3 nanocomposites reinforced with sub-micron Ni and NiAl2 O4 .
Mater. Sci. Eng. A 2001, 302, 83–91. [CrossRef]
61. Oleszak, D. NiAl-Al2 O3 intermetallic matrix composite prepared by reactive milling and consolidation of powders. J. Mater. Sci.
2004, 39, 5169–5174. [CrossRef]
62. Konopka, K.; Krasnowski, M.; Zygmuntowicz, J.; Cymerman, K.; Wachowski, M.; Piotrkiewicz, P. Characterization of Al2 O3
samples and NiAl-Al2 O3 composites consolidated by Puls Plasma Sintering. Materials 2021, 14, 3398. [CrossRef]
63. Travitzky, N. Processing of ceramic-metal composites. Adv. Appl. Ceram. Struct. Funct. Bioceram. 2012, 111, 286–300. [CrossRef]
64. Chevalier, J.; Gremillard, L.; Virkar, A.V.; Clarke, D.R. The tetragonal –monoclinic transformation in zirconia: Lessons learned and
Future trends. J. Am. Ceram. Soc. 2009, 92, 1901–1920. [CrossRef]
65. Lin, K.-L.; Lin, C.-C. Reaction between titanium and zirconia powders during sintering at 1500 ◦ C. J. Am. Ceram. Soc. 2007, 90,
2220–2225. [CrossRef]
66. Rocha-Rangel, E.; Rodriguez-Garcia, J.A.; Esparza-Vazquez, S.; Cruz-Sanchez, B.; Estraada-Guel, I.; Martinez-Sanchez, R. Effect of
particle size and titanium content on the fracture toughness of particle-ceramic composites. Mater. Today Proc. 2016, 3, 249–257.
[CrossRef]
67. Niihara, K.; Nikahira, A.; Sekino, T. New composites structural ceramics. Mat. Res. Soc. Symp. Proc. 1993, 289, 405–412.
68. Kim, D.-K.; Kriven, W.M. Processing and characterization of multiphase ceramic composites Part II: Triplex composites with a
wide sintering temperature range. J. Am. Ceram. Soc. 2008, 91, 793–798. [CrossRef]
69. Łada, P.; Miazga, A.; Wożniak, J.; Konopka, K.; Olszyna, A. The formation of ZrO2 -Ti composites by spark plasma sintering.
Powder Metal. Met. Ceram. 2017, 55, 644–649. [CrossRef]
70. Zygmuntowicz, J.; Konopka, K.; Krasnowski, M.; Piotrkiewicz, P.; Bolek, J.; Wachowski, M.; Żurowski, R.; Szafran, M. Characteri-
zation of Al2 O3 matrix composites fabricated via the slip casting method using NiAl-Al2 O3 composite powder. Materials 2022,
15, 2920. [CrossRef]