Hydrothermal Synthesis

Ender Suvaci and Emel Özel, Eskisehir Technical University, Eskisehir, Turkey
r 2020 Elsevier Inc. All rights reserved.

Powder Synthesis Methods

Particulate materials play significant roles in technological developments and subsequently impact our daily lives. Their physical
and chemical characteristics significantly affect their functionality properties and performance (Adair and Suvaci, 2000). Therefore,
it is critical to control particle characteristics to fulfill the expectations of future technologies. Moreover, such particulate materials
can exhibit novel properties by tailoring its physical characteristics. For example, when their size goes down to nanoscale then they
demonstrate unique properties or particles with anisometric (plates, rods, etc.) morphology enable researchers to have access to
novel anisotropic properties via texture development in advanced ceramics (Messing et al., 2004; Suvaci and Ozer, 2005).
Therefore, the powder synthesis methods should enable one to tailor the physical properties of particles.
The most widely utilized nonmetallic inorganic powder synthesis methods are mixed oxide solid-state reaction, liquid phase based
methods such as coprecipitation and hydrothermal synthesis, and gas phase based methods such as vapor-phase reaction. Although the
solid-state method is commonly used for powder synthesis, this method has many drawbacks such as low purity, large particle size, and
broad particle size distribution. The vapor phase methods provide high purity powders but stoichiometry of the resultant particles can
be poor and they exhibit usually high degree of aggregation. On the other hand, the liquid based methods can lead to improved control
of the thermodynamics and kinetics involved in nucleation and growth processes. Therefore, growing particles of varied morphologies
in those methods can be achieved by altering thermodynamic and kinetic parameters such as temperature, concentration of reactants,
duration of crystal growth, and additives (Ring, 1996). High purity and better stoichiometry control are provided with the copreci-
pitation method; however, wide particle size distribution can be formed from submicron to micron size (Adair and Suvaci, 2001). Since
the precipitation phase in aqueous media is usually not oxides but its hydrates, it should be calcined to achieve the final form prior to
use of such particles and unfortunately this calcination step results in aggregation of fine particles. As a result, most of such powders
should be milled to achieve fine particle size. Among the synthesis methods, hydrothermal synthesis has been widely utilized because it
leads to powder with superior properties such as high purity, phase stability (stoichiometry), tailorable particle size, and narrow size
distribution, and controllable morphologies depending on technological developments and hence demands in particle technologies.
Hydrothermal synthesis involves direct formation of crystals from solutions in aqueous media at elevated temperature (T 4 251C) and
pressure (4100 kPa). In this method, powders nucleate and grow in a controlled manner and subsequently result in crystallized
particles with controlled size and morphology as well as low degree of aggregation/agglomeration. As an example, Fig. 1 shows various
oxide particles with various morphologies spanning from cubes to rods synthesized by hydrothermal methods. In addition, coating of
particles can be achieved by using hydrothermal synthesis to improve particle characteristics or to add new functionality to the substrate
particle as shown in Fig. 2 where PbTiO3 platelet is coated with BaTiO3 particles. Besides allowing controllable material characteristics
with stoichiometry, hydrothermal synthesis offers additional substantial benefits such as operating at low synthesis temperature, fast
and flexible continuous or batch processing, large scale industrial production, cleaner processing routes, and not involving harmful
organic solvents. In addition, energy consuming steps such as high temperature calcination and milling are not needed in this process.
Consequently, hydrothermal synthesis can be considered as a green and energy efficient process. The assessment of the powder synthesis
methods according to obtained particle characteristics are presented in Table 1.

Recent Activities in Hydrothermal Synthesis

Recently, various synthesis strategies for precise control of the hydrothermal synthesis conditions have been developed in order to
tailor synthesised product characteristics in terms of size, shape and composition (Feng and Li, 2017). These strategies consist of
internal factors related to the reaction system such as use of organic additives, templates, and substrates and the external
environment’s effects including but not limited to utilization of microwaves, electric field, or magnetic field during hydrothermal
synthesis to get desired materials structure forms (Yang and Park, 2019). Such developments also contributed to earlier hydro-
thermal-based synthesis types and now hydrothermal synthesis has been used in many different forms as depicted as hydro-
thermal synthesis tree in Fig. 3.
During the last two decades, hydrothermal synthesis has become the key synthesis method for powder materials to obtain unique
properties by tailoring their physical characteristics. Fig. 4. shows the number of publications on the hydrothermal synthesis for each
year beginning from 2000. The data were collected from the Web of Science by using the key words hydrothermal and synthesis. As shown
in Fig. 4, the number of published papers steadily increased to 2014; since then there has been a slight decrease but the numbers are still
high. Accordingly, the total number of publications on hydrothermal synthesis since 2000 to date exceeds 11,000.
Among those published papers, an increasing number about continuous hydrothermal synthesis is very remarkable. More
recently, scientists have worked diligently to demonstrate potential use of rapid continuous hydrothermal methods for production
of inorganic materials. With continuous hydrothermal synthesis, manufacture of various nanomaterials can be scaled up for

Encyclopedia of Materials: Technical Ceramics and Glasses doi:10.1016/B978-0-12-803581-8.12096-X 1

2 Hydrothermal Synthesis

Fig. 1 Scanning electron microscopy images of various oxide particles with various morphologies synthesized by hydrothermal method: (a) Cubic
Pb(Zr0.52Ti0.48)O3 particles, (b) plate-like PbTiO3 particles, and (c) rod-like ZnO particles.

Fig. 2 Scanning electron microscopy image of BaTiO3 coated PbTiO3 platelets.

commercial applications with controllable particle properties (stoichiometry, size, shape, porosity, etc.). The latest progress in
continuous hydrothermal techniques was presented recently by some research groups (Dunne et al., 2015; Darr et al., 2017).
To investigate the impact of the external environment’s effects on the synthesis and the properties of the nanomaterials such as
semiconducting nanomaterials, scientists have designed and developed microwave, electric field, and magnetic field assisted
hydrothermal methods. The increase in number of the published papers on microwave assisted hydrothermal synthesis sorted by
year is shown in the inset in Fig. 4. Although there are a limited number of papers (o15) on magnetic and electric field assisted
hydrothermal synthesis, the number of publications on microwave assisted hydrothermal synthesis exceeds 115 in 2019 alone.
Similar to the publication numbers of papers, 141 patents on microwave assisted hydrothermal synthesis, 37 patents on con-
tinuous hydrothermal synthesis, 9 patents on magnetic field assisted, 1 patent on electric field assisted hydrothermal synthesis
have been published since 2000. Consequently, large numbers of published papers and patents on hybrid hydrothermal synthesis
have been issued by companies and scientists to improve both powder properties and process efficiency.
 Hydrothermal Synthesis 3

Table 1 Particle characteristics depending on the powder synthesis methods

Powder Synthesis methods Size Morphology control Stoichiometry Purity Aggregation

Solid-state reaction (mixed-oxide) Coarse (micron) Poor Poor Low Yes

Coprecipitation Coarse (submicron–micron) Medium Good Medium Yes
Sol–gel Fine (nanosubmicron) Medium Good High Yes
Molten flux Coarse (micron) Medium Medium Low No
Vapor phase Fine (nanomicron) Medium Poor High Yes
Hydrothermal Fine (nanosubmicron) Good Good High No

Note: Compiled from Adair, J.H., Suvaci, E., 2001. Submicron electroceramics powder by hydrothermal synthesis. In: Buschow, K.H.J, Cahn, R.W., Flemings, M.C, et al. (Eds.), Encyclopedia
of Materials: Science and Technology, second ed. Amsterdam: Elsevier. Phanichphant, S., Heimann, R.B., 2004. Hydrothermal synthesis of submicron- to nano-sized ferroelectric powders:
Properties and characterization. CMU Journal 3 (2), 113–132. Yoshimura, M., Byrappa, K., 2008. Hydrothermal processing of materials: Past, present and future. Journal of Materials Science
43, 2085–2103. Shandilya, M., Rai, R., Singh, J., 2016. Review: Hydrothermal technology for smart materials. Advances in Applied Ceramics 115 (6), 354–376.

Fig. 3 The hydrothermal synthesis tree, which shows branches of hydrothermal synthesis reported in the literature to date.

Among these hybrid hydrothermal methods, the microwave assisted hydrothermal synthesis has had high research interest in
recent years. Compared with the traditional hydrothermal method that performed in relatively high reaction temperature dif-
ferences and long reaction time, the microwave hydrothermal method gives ultrafine nanoparticles with narrow particle size
distribution and uniform morphology by applying a fast and uniform heating system. Recently, hydrothermal powder synthesis
and its applications for smart materials were reviewed by Shandilya et al. (2016) where they focused on process definitions,
technological merits, and current applications. In another study, Yang and Park (2019) reviewed the developments on the
conventional and microwave hydrothermal methods, their reaction mechanisms, and practical applications of the two methods.

General Principles and Equipment

In hydrothermal synthesis, chemical reactions of substances take place in a sealed and heated aqueous solution at elevated temperatures
(T 4 251C) and pressures (P 4 100 kPa) to form crystalline materials directly from solution. In this method, pressures as high as
500 MPa and temperatures up to 10001C can be utilized to enhance dissolution of reactants and subsequently the nucleation and
growth of certain types of materials such as single crystals of oxides, diamond, or carbon nanotubes (Suchanek et al., 2004). If the
4 Hydrothermal Synthesis

Fig. 4 The number of publications on hydrothermal synthesis for each year beginning in 2000. The data were collected from the Web of Science
by using key words hydrothermal and synthesis.

synthesis takes place in a nonaqueous solution with organic solvents at relatively high temperature, it is called solvothermal synthesis.
There are different forms of solvothermal synthesis based on the solvent type, such as alcohols, glycols (i.e., ethylene glycol, diethylene
glycol, triethylene glycol) or oleylamine (OAm). For example, the solvothermal method is called glycothermal synthesis when glycols
such as ethylene glycol or 1,4-butanediol are used as solvents (Adair and Suvacı, 2001) whereas it is called alcohothermal synthesis
when alcohols (e.g., ethanol) are used.
In hydrothermal and solvothermal systems, sealed container (reactor or autoclave) or high-pressure autoclave is used under
subcritical or supercritical conditions of the solvent. The pressure developed in an autoclave is related with the filling volume
(typically maximum filling volume is 70% of the autoclave capacity to assure the process safety). In most cases, reactors are metal
autoclaves such as stainless steel or high-strength alloys with Teflon or alloy linings. Teflon inserts are commonly used in
autoclaves up to 2001C and 20 MPa synthesis conditions because they are inert to both acidic and alkaline media compared with
glass and quartz inserts. In the case of Teflon uses at T 4 2001C, Teflon can creep and this can cause undesired problems. In such
cases, other alternative materials such as high-strength alloy autoclaves with tubes made from platinum, gold, or silver are utilized
to protect the autoclave body from the corrosive solvents or ingredients (Li et al., 2015).

Approaches for Hydrothermal Synthesis

There are several steps that should be considered for achieving desired powder characteristics in hydrothermal synthesis process.
The algorithm for a hydrothermal synthesis shown in Fig. 5 demonstrates a general perspective for hydrothermal synthesis
application to achieve target material properties.

What is the Nature of the Material?

Before starting synthesis of any materials, the nature of the materials to be synthesized should be known and their expected
properties should be identified or listed. It is essential to understand the materials properties to optimize or control their particle
features. Material properties can be classified as chemical properties, physical properties, colloidal properties, electronic properties,
and optical properties (Adair et al., 1988, 1998). The critical chemical properties such as phase equilibria and solubility are
necessary to control phase purity. The physical properties such as crystal structure and equilibrium crystal shape, dictated by
surface energies of crystallographic plane, are important to control the morphology of particles. The colloidal properties include
surface groups, hydrophilicity, isoelectric point, Hamaker constant, etc., and they are useful to control to dispersion of particles in
solutions or preventing agglomeration of particles. Since the attractive van der Waals forces among the particles result in
agglomerated particles, they can also affect electrical properties (e.g., dielectric constant, dielectric dispersion, ferroelectricity,
piezoelectricity, ferromagnetism) and optical properties (e.g., band gap, absorption spectra) (Adair et al., 1988, 1998).
 Hydrothermal Synthesis 5

Fig. 5 Algorithm for a hydrothermal synthesis.

What are the Expected Powder Characteristics?

The powder characteristics that can control properties and performances of particulate materials are stoichiometry, phase stability, size, size
distribution, morphology, purity, and degree of agglomeration. To establish phase stability, combinatorial routes for phase development
can be applied, dissolution and phase changes are evaluated, and process variables such as degree of supersaturation, solution pH, and
temperature should be employed. The control over size of the particles can be achieved by degree of supersaturation control, nuclei
concentration, homogeneity of solution, and solution properties such as viscosity, ionic strength, etc., as described in the mechanism
section below. In the case of the morphological control for particles, surface equilibria, complexing agent, and surface electrostatic features
play important role during hydrothermal synthesis. To prevent aggregation, surface charge of particles must be controlled and interaction
energies, van der Waals and polarization forces and organic adsorbates should be considered (Adair et al., 1988, 1998).
The hydrothermal method allows controlling of material characteristics with stoichiometry. Therefore, this method is often chosen
to synthesize or produce different types of nanomaterials such as silicates, zeolites, oxides, ceramics, metals, alloys, composites, and so
on. These materials can be in variety of forms such as equiaxed (e.g., cubes, spherical), elongated (fibers, whiskers, nanorods, nano-
tubes), plates, etc., as shown in Fig. 1. With hydrothermal synthesis, particle size and morphology characteristics can be manipulated
over a wide range. For example, whiskers, plates, or cubes can be oriented to form materials with single crystallite like properties, such as
textured ceramic–ceramic composites with anisotropic properties (Suchanek and Riman, 2006). Recently, much effort has been devoted
to improve physical, chemical, and electrical properties of nanomaterials by designing of these material characteristics. For example, as
anode material, Zn2SnO4 particles with high purity, smaller particle size, and uniform morphology have the best properties for Li ion
batteries. With improving physical properties and morphological structures of Zn2SnO4 materials, battery performance and the elec-
trochemical performance can be enhanced with hollow cube structure compared with dispersed single crystal cubes (Zhao et al., 2016).

Surface and Colloid Chemistry of the Material in Aqueous Media

Water is an environmentally safe material and cheaper than other organic solvents and thus it is much more widely utilized in
hydrothermal synthesis compared with organic solvents. Frank (1978) summarized the physical and chemical properties of water
dependent pressure and temperature (PT) data under hydrothermal conditions. These data and other physical properties for water up to
10001C and 1000 MPa are well known (Byrappa and Yoshimura, 2001). Under high temperature and pressure conditions in an
autoclave, the density, surface tension, and viscosity of water will be lower resulting in significantly higher ionic and molecular mobility
than at ambient conditions (Feng and Li, 2017). Therefore, since solvent properties of water under high temperature and pressure can be
considerably changed, using of pressure and temperature diagram of the water effectively is very important for understanding the
hydrothermal synthesis better. Because of the increased ionization of water caused by increased temperature, the ionic or chemical
reactions of the indissolvable inorganic materials can be promoted under hydrothermal condition at the high temperature and pressure.
Another important issue of hydrothermal synthesis is to understand the surface and colloid chemistry of materials in an aqueous
reaction medium. When metal oxide based powders are immersed into water, surface charge develops on the particles. The most
important charging mechanism for these systems are (1) the dissociation of the surface to yield an ion (usually a proton) to the
solution; (2) Nernstian charging through specific adsorption or desorption of lattice ions; (3) metal hydrolysis via ionization of the
6 Hydrothermal Synthesis

particle surface due to protonation or deprotonation of acid or basic surface groups; and (4) incongruent dissolution (leaching).
Mechanism 3 is commonly observed for all metal oxides (except silica) and metal hydroxides. Solution pH is the most critical solution
feature, which can be used to change surface charge. Mechanism 4 involves metal hydrolysis with incongruent dissolution of the at least
one of the cationic species (Adair et al., 2001). Especially, final mechanism is critical to mixed metal (multication) oxide systems.
Therefore, during in situ transformation of powder from precursor solution or precipitation–recrystallization in aqueous media, cation
concentration must be under control to conserve stoichiometry of each component because of the such colloidal interactions between
particles and water molecules. This has been shown by Tuncolu et al. (2015) where excessive Zn2 þ dissolution during washing of the
precipitated Zn2SnO4 phase results in difficulty in stoichiometry control.

Evaluation of the Solubility–pH Diagrams in Aqueous System

Evaluation of the solubility-pH diagram is another important issue for understanding dissolution-reprecipitation behavior of metal salts
depending on concentration, pH of solution, and temperature. When suspended particles dissolve into solution, they supersaturate the
solution and then dissolution-recrystallization is observed and consequently particles precipitate in the solution. Solubility limits of starting
metal oxide salts and solubility behavior of materials will change depending on pH and concentration in reaction solution and subse-
quently they will affect. Thus, assessment of the solubility-pH diagram will help to choose appropriate initial concentration of cations and
pH of the reaction medium. For example, Since Zn2 þ solubility is greater than Sn4 þ solubility; in our earlier studies, to achieve
stoichiometric Zn2SnO4 particles, excess Zn2 þ (i.e., Zn2 þ /Sn4 þ ¼ 2.4 instead of Zn2 þ /Sn4 þ ¼ 2.0) should have been added to system
prior to hydrothermal synthesis at pH 8.0 (Tuncolu et al., 2015). In the case of the limiting solubility in water, mineralizers such as pH
adjusting agents (e.g., acids or bases) or the complexing agents can be added to enhance the solubility in water. When starting materials
have higher solubility and difficulties in the control of dissolution-recrystallization in aqueous media, solvothermal synthesis can be
considered with organic solvents. On the other hand, in hydrothermal synthesis, some materials such as barium titanate or hydroxyapatite
often can exhibit water related lattice defects or poor stoichiometry. For example, in barium titanate synthesis, hydroxyl ions substituted for
oxygen ions generate barium ion vacancies, which degrade the dielectric properties; in hydroxyapatite synthesis, poor control of its calcium
stoichiometry can be observed at presence of residual water (Suchanek et al., 2004). In such cases, the problem of water incorporation can
be overcome by either adjusting synthesis conditions or by using of solvothermal processing with nonaqueous solvents.

What are the Thermodynamics and Kinetic Variables for the Hydrothermal Synthesis?
Thermodynamics and kinetic variables are the key parameters that control the hydrothermal synthesis and hence final product
characteristics. Therefore, these variables should be evaluated for the materials system in detail prior to hydrothermal synthesis.
The thermodynamic process variables are concentration of reactants and additives, temperature and pH of solution (Suchanek and
Riman, 2006). These parameters influence both reactor and crystallization kinetics. Crystal morphology and size can be modified
by surfactants that can adsorb on specific crystallographic faces (Ring, 1996). Size of the crystals and phase purity can be controlled
by varying temperature and concentration (Tuncolu et al., 2015) Mass transport process and kinetics of chemical reactions
generally increase in magnitude with increasing temperature. Mass transport process and chemical reaction rates generally increase
in magnitude with increasing temperature. Since the kinematic viscosity for hydrothermal solution is approximately one order of
magnitude lower in aqueous media than that for the gas phase. As a result, the hydrothermal synthesis conditions allow fast
transport and high dissolution rates. Since the effect of pressure on the viscosity is significant only above the critical points of
temperature and pressure, mass transport process and chemical reaction rates do not change with pressure during typical
hydrothermal synthesis where usually temperature and pressure are below the critical values. The influence of pressure on the
process is observed when the pressures exceeds 100 MPa and only at T 4 3001C (Suchanek and Riman, 2012).
If the thermodynamic variables are limited to achieve the desired morphology and size control, nonthermodynamic variables
such as stirring can be employed to enhance uniformity and the control over the particle formation process. Previous studies
showed that the stirring speed can be varied to change morphology of the particles during the hydrothermal synthesis. Potential
segregation problems that can be caused by concentration and temperature gradients or low heating rates can be prevented by
stirring (Suchanek and Riman, 2012).

Powder Synthesis via Hydrothermal Method

In practice, a typical powder synthesis via hydrothermal method usually involves four important stages including selection of
precursor, precipitation and gel formation, removal of undesired species, and hydrothermal reactions. Fig. 6 shows the steps of
hydrothermal synthesis as a flow chart.

Selection of Precursors
In hydrothermal synthesis, many types of precursor such as aqueous solution of dissolved salts, aqueous dispersion of solids
(suspensions), or precipitated colloidal dispersion (gel precursors) are used. Metal salts such as nitrates, chlorides, sulfates,
 Hydrothermal Synthesis 7

Fig. 6 Stages of the hydrothermal synthesis.

acetates, etc., have solubility in aqueous media and are generally used as a starting material. Inexpensive precursor compounds,
easy to handle chemicals, and compounds that react cleanly to form the product are desired. When choosing metal salts as a
starting material, the role of released ions on the purity, size, and morphology of synthesized powders should be considered.
Detailed recommended features for different type of precursors to provide reasonable yields of product were already reported in
previous studies (Adair et al., 1988, 1998). In one of the earlier studies, the effect of the precursor type on the morphology of the
hydrothermally synthesized ZnO particles was evaluated by using ZnCl2 and Zn(NO3)  6H2O precursors (Ozel et al., 2016). It has
been shown that during hydrothermal synthesis of ZnO particles, particle size and morphology of ZnO crystals were affected from
precursor type and initial concentration that result in change in growth mechanisms such as classical nucleation growth or Ostwald
ripening. When ZnCl2 was used as precursor, agglomerated ellipsoidal rod like morphology was formed with classical nucleation
growth mechanism whereas flower like morphology was obtained by using Zn(NO3)  6H2O precursor via Ostwald ripening for
the initial concentration range between 0.25 and 1 M.

Preparation of Gels
n addition to solutions and dispersions, precipitated intermediate forms such as gels or sols are frequently used as precursors in
hydrothermal synthesis. Gel formation can be achieved by either homogeneous precipitation or direct strike precipitation
methods. In the homogeneous precipitation technique, the precipitation occurs homogeneously due to uniform pH change in the
solution, where homogeneous precipitation agents such as urea and hexamethylenetetramine are activated by heating or using
enzymes. On the other hand, in the direct strike precipitation method, direct addition of acids or bases into the solution results in
precipitation. Since the pH change in the solution is much more uniform, the gel structure is usually more homogeneous in the
homogeneous precipitation with respect to that of the direct strike precipitation. However, the direct strike precipitation is readily
applicable and can be used at high molarity levels while the homogeneous precipitation is only suitable at relatively low
concentrations.

Removal of Undesired Species

In hydrothermal synthesis, the chemical purity of the powder materials is higher due to starting with high purity precursors.
During crystallization processes, growing crystals/crystallites tend to reject impurities present in the growth environment. There-
fore, it is expected that impurities such as ions come from metal salts or pH adjusting agents remove from the system together with
8 Hydrothermal Synthesis

the crystallization solution. However, some of them can be adsorbed to particle surface due to the colloidal interactions between
particles and present ions. If high purity in the synthesis powder is the target to obtain excellent physical properties and high
material performance, two steps hydrothermal synthesis must be considered to removing of undesired species comes from metal
salts by washing with pH adjusted water rather than using one step hydrothermal synthesis that involves direct feeding of the gel
prepared above and its supernatant to the to the autoclave without separating the gel and supernatant (Tuncolu et al., 2015). For
example, high purity Zn2SnO4 powder via hydrothermal method was synthesized by removing anions with pH adjusted water to
obtain better ceramic target performance to develop thin film for transistor channels.

Additives
The varieties of synthesis precursors, mineralizers, and additives such as organics, complexing agents, surfactants, or adsorbates
offer more room for design the material characteristics. Mineralizers are either inorganic or organic additives and are often used to
adjust pH and improve solubility. In addition, there are other additives that are used to promote particle dispersion or control
crystal morphology. Complexing agents can establish morphological control for particles. Surfactants and organic adsorbates
prevent aggregation of particles (Adair et al., 1988, 1998). Recently, in a review article, Shi et al. (2013) demonstrated utilization of
four hydrothermal synthesis approaches (i.e., organic additive-assisted, organic additive and template free, template assisted, and
substrate assisted hydrothermal syntheses) to control particle size and morphology effectively during the hydrothermal synthesis
of inorganic semiconducting nanoparticles.

Mechanisms

Powder synthesis during hydrothermal process involves utilization of precursors. Such precursors can be sols, gels, or suspensions.
Conversion of such precursors to powder can occur via either in situ transformation or dissolution-reprecipitation mechanisms. In the
former, characteristics of the precursor can dictate the powder characteristics, whereas, in the latter mechanism, precursor is completely
dissolved and then precipitates in powder form. Therefore, precursor characteristics are not transferred directly to the powder during this
mechanism. It should also be noted that as mentioned above regardless of mechanisms, powder formation can still be kinetically
controlled by chemical characteristics of the precursor such as ion release rate, formation of less soluble intermediate phases, etc. Besides
precursor type and concentration, the morphology of the ZnO crystals is also influenced by pH of the solution and used alkaline
solutions such as KOH, NaOH, or NH4OH. For example, Podlogar et al. (2016) showed that the resulting morphology of the ZnO with
different shapes and crystal sizes can be achieved by altering the pH of the suspension with NaOH solution after the precipitation.
Depending on the ratio of Zn2 þ /OH ions in the starting solutions, rods or branched clusters composed of rod-like crystals were
observed after the hydrothermal treatment of pure Zn(OH)2 at the highest ratio of Zn2 þ /OH ions of 2.5 whereas petal-like ZnO
crystals precipitated from the solution and only coarsened at the expense of dissolved Zn(OH)2 by lowering the Zn2 þ /OH ion
concentration and sphalerites-like ZnO precipitated at the lowest Zn2 þ /OH ratio of 0.1.
Final powder characteristics, particularly size and morphology, are directly determined by nucleation and growth kinetics
during hydrothermal synthesis. According to the classical nucleation and growth theory, as cation concentration increases number
of nuclei increases due to higher saturation and nucleation frequency and hence particle size decreases. However, if some of the
nuclei are too small to survive, they dissolve and increase the saturation level so that other relatively larger nuclei grow at the
expense of those fine nuclei. Such growth process is called Ostwald ripening. In such systems, particle size increases as cation
concentration increases. It has been shown that there is a critical cation concentration (CCC) for the hydrothermal systems at
which nucleation and growth mechanism changes. While the mechanism described by Ostwald ripening is effective at con-
centrations below the CCC, classical nucleation and growth theory is effective at concentrations greater than the CCC (Fig. 7). The
CCC is a function of temperature, pH, pressure, concentrations of other ions and all other processing parameters that can affect
solubility of the powder constituents in particular cations. Aciksari et al. (2016) showed that for hydrothermal synthesis of SnO2,
the CCC was 0.1 M.
The growth process determines the final particle size during hydrothermal synthesis. The growth rate is controlled by either diffusion
or interface reaction. The growth mechanism can be determined by using LSW (Lifshitz, Slyozov, and Wagner) theory where
rn  r n0 ¼ kt
where, r is the average particle size at time t; r0 is the average initial particle radius; k is rate constant; t is the allowed time for the growth;
and n is the constant describing the mechanism. If n ¼ 2, the growth is controlled by interface reaction whereas if n ¼ 3 then diffusion
is the rate controlling mechanism. Since determination of the mechanism enables one to tailor the processing parameters to achieve the
targeted particle characteristics, such understanding can also enhance the predictability of the final powder characteristics.

Modeling

Like all well-developed industrial processes, to make hydrothermal synthesis one of the most preferred and widely used powder
synthesis methods by the industry, it should be possible to predict the product and its characteristics as a function of critical
 Hydrothermal Synthesis 9

Particle size (d)

Particle size (d)

Cation Concentration (C) Cation Concentration (C)

Ostwald ripening Classical nucleation theory

CCC= f (pH, T, P, other ion concentration)

Initial Cation Concentration (C)
CCC= Critical cation concentration

Fig. 7 Effect of the initial cation concentration on the growth mechanism during the hydrothermal systems.

processing parameters without requiring many trial and error type experiments. This can only be achieved by modeling hydro-
thermal processes where thermodynamic and kinetic effects play critical roles on the powder characteristics. Therefore, many
researchers have involved in modeling hydrothermal synthesis so that it will be one of the mainstream particle synthesis
technologies.
In early attempts, hydrothermal synthesis was modeled based on the thermodynamic criteria for ideal solutions to predict
phase stability diagrams for the systems under investigation (Baes and Mesmer, 1976; Adair et al., 1988, 1998). However, since the
precursor concentrations and corresponding powder yields are not specified by such phase stability diagrams, it was proposed to
use of yield diagrams that demonstrate specific synthesis conditions to achieve precipitation of the phase of interest, quantitatively
(Lencka and Riman, 1993). Phase stability and yield diagrams are calculated based on a thermodynamic model that follows the
Helgeson–Kirkham–Flowers–Tanger equation. This equation uses activity coefficients to predict standard state properties of
aqueous species with a nonideal solution model. Methodology for generating phase stability and yield diagrams was discussed by
Suchanek et al. (2004) in an earlier publication.
Although thermodynamically derived phase stability and yield diagrams are very critical to understand the roles of con-
centration, temperature, and pressure on the final phase, as well as effects of precursor type on final powder characteristics and the
cost, there are other phenomena such as hydrothermal reaction rate, particle size, and morphology development that are con-
trolled by kinetic factors. Therefore, in addition to thermodynamic modeling, kinetic models that can predict the reaction rate,
particle size, and morphology should be developed. Although the thermodynamic models are mature and their high prediction
capability for some specific systems has been successfully shown, the kinetic models are not mature enough yet and hence they still
need to be improved. Accordingly, to engineer hydrothermal reactions after the phase stability and the yield diagrams are
established for the materials of interest, hydrothermal experiments should be designed to test and validate the calculated diagrams
and after the validation experiments the processing variable-phase maps can be generated and they can be used to predict
hydrothermal reaction and crystallization kinetics (Suchanek and Riman, 2012).

References

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