Author's Accepted Manuscript

Recent development on preparation of ceramic inks

in ink-jet printing
Zhidong Pan, Yanmin Wang, Huining Huang,
Zhiyuan Ling, Yonggang Dai, Shanjun Ke

www.elsevier.com/locate/ceramint

PII: S0272-8842(15)01240-7
DOI: http://dx.doi.org/10.1016/j.ceramint.2015.06.124
Reference: CERI10863

To appear in: Ceramics International

Received date: 22 May 2015

Revised date: 25 June 2015
Accepted date: 26 June 2015

Cite this article as: Zhidong Pan, Yanmin Wang, Huining Huang, Zhiyuan Ling,
Yonggang Dai, Shanjun Ke, Recent development on preparation of ceramic inks in ink-
jet printing, Ceramics International, http://dx.doi.org/10.1016/j.ceramint.2015.06.124

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Running head: Preparation of ceramic inks 1

Recent development on preparation of ceramic inks in ink-jet printing

Zhidong Pana, b, Yanmin Wang a*, Huining Huangb, Zhiyuan Linga, Yonggang Dai b,

Shanjun Kea

(a School of Materials Science and Engineering, South China University of

Technology, 510640, Guangzhou, China; b Guangdong KITO Ceramics Co., Ltd.,

528031, Foshan, China)

Abstract

The ink-jet printing has been widely applied in the decoration of ceramic tiles in

last ten years since its excited characteristics provide the possibility to produce the

customized ceramic tiles with higher image definition at a lower cost in a shorter

duration. The number of ink-jet printers in operation worldwide increased rapidly in

recent years. Besides the printer, one of the critical factors for an effective printing is

inks. This paper focuses on the ceramic ink and reviews recent development on the

preparation of ceramic inks by various methods, such as sol-gel, reverse

microemulsion, polyol, hydrothermal and mechanical grinding. Some aspects for

future development are proposed based on the application of ceramic inks in

industries.

Key words: Ceramic; ink-jet; ink; preparation

1 Introduction

Ink-jet printing has been developed as a non-contact direct-write technology for

the decoration of ceramic tiles [1–6]. Since 2000, the ink-jet printing for the

decoration of ceramic tiles has attracted recent attentions. The conventional printing

processes used for ceramic tile decoration are flat screen printing in the 1960s,

rotary screen printing in the 1970s and flexographic and intaglio printing in the 1990s

[7]. It is necessary for the printing with the conventional methods above to contact

the printer with ceramic tiles. However, ink-jet printing as a non-contact deposition

method can provide a low-cost, high-definition, efficient use of materials and waste

elimination process. Also, the contamination is minimized in ink-jet printing.

1.1 Characterization of ink-jet printing

As a promising technique, ink-jet printing is suitable to produce complex

patterns. All ink-jet printing techniques are based on the digitally controlled ejection

of drops of fluid from a print head onto a substrate. The ink-jet printers are classified

as either continuous (CIJ) or drop-on-demand (DOD) [8]. The drop-on-demand (DOD)

mode is widely applied in ink-jet printing for various industrial applications, which

deposits a precise quantity of functional ink in the form of droplets on a substrate.

The inks consist of a solute dissolved or dispersed in a solvent. The process

essentially involves the ejection of a fixed quantity of ink in a chamber, from a nozzle
through a sudden, quasi-adiabatic reduction of the chamber volume via piezoelectric

action. A chamber filled with liquid is contracted in response to application of an

external voltage. This sudden reduction sets up a shockwave in the liquid, which

causes a liquid drop to eject from the nozzle. The ejected drop falls due to gravity

and air resistance until it impinges on the substrate, spreads under momentum

acquired in the motion, and surface tension aided flow along the surface. The drop

then dries through solvent evaporation [9]. In addition, a direct-write technique

named electrohydrodynamic printing was developed to perform ceramic patterns,

such as nano-sized hydroxyapatite, lead zirconate titanate (PZT), etc., with a higher

resolution when compared to conventional ink-jet printing [10–12].

In recent years, the ink-jet printing applied in the decoration of ceramic tiles has

become more popular. Many manufacturers have adopted the ink-jet printing to

produce patterns on the ceramic tiles since the ink-jet technique has the following

advantages:

a) The ink-jet printing is a non-contact method with a lower noise, compared to

the conventional printing techniques. The sole forces that are applied to the

substrate result from the impact of tiny ink drops. Hence, fragile substrates and

non-flat substrates, which are difficult to be treated in the conventional printing

methods, can be processed.

b) The ink-jet printing is a totally digital process. The process from design to

product is simplified, leading to the time saving and lower details loss. It is effective

for the ink-jet printing to obtain the high image definition and the better image
performance. The location of each droplet of inks deposited on the substrate can be

predetermined and also can be changed in real time. Hence, the different patterns of

tile can be processed in sequence or even together. The ink-jet printing provides a

more realistic representation of natural material such as stone and wood. It is

possible for the ink-jet printing to produce the customized products with a lower cost

in a shorter duration, compared to the conventional processes. The edge-to-edge

printing in ink-jet printing allows the uninterrupted patterns across tile boundaries.

c) A wider color gamut is performed in ink-jet printing by using the inks of

different colors, such as the standard four colors (i.e., cyan, magenta, yellow and

black) and six colors.

d) The use of inks (ceramic colorants) is more efficient.

e) A wide range of materials can be deposited. The material is in a liquid form

with its physical properties (i.e., mainly viscosity and surface tension) lying in an

appropriate range. Pigments, dyes, glass frits and metallic particles are readily

printed from suspensions, as well as a wide range of other materials, which can be

used to perform optical and electronic functions.

f) The machine footprints for the ink-jet printing are smaller than those for the

conventional processes [6,13–15].

1.2 Inks

Some dominant factors affecting an effective printing process are the printer

performance, ink properties and substrate characterization. The physical and

chemical properties of inks are the critical parameters in ink-jet printing, which have

a great influence on the generation of ink droplets, the interaction between ink

droplets and substrate, and drying of ink droplets to form a pattern. For applications,

the ink chemistry that directs the hardware selection and drives the implementation

should be defined. There are four major types of ink-jet inks, i.e., phase-change,

solvent-based, water-based, and UV curable. Some inorganic materials such as ZrO2,

Al2O3 and Pb(Zr0.53Ti0.47)O3 (PZT) were applied in the phase-change inks. Meanwhile,

Au/Cu, BaTiO3, ZrO2, NiO and ceramic pigments in the solvent-based inks can be used

in ink-jet printing. Solvent-based inks use alcohol or a mixture of alcohols such as

ethanol, isopropanol, 2-methoxyethanol and terpineol as a vehicle. It is necessary for

the drying of UV curable inks to use UV radiation [8,16–25].

The preparation of the inks is often complicated due to the challenging

requirements of ink-jet inks. Except for the conventional requirements （i.e., long
shelf life and proper color properties ）, the inks must possess the physico-chemical
properties that are specific to the various printing situations. The effect of each

component of the ink on the overall performance, from storage in the cartridge,

through jetting, to its behavior on the substrate and on human health and

environment should be evaluated. The factors like ink stability, viscosity, surface

tension, pH value and electrolytes, dye/pigment content, solid loading, foaming and

defoamers have to be considered in the process of formulating a ink [8,26].

2 Decoration of ceramic tiles by ink-jet printing

Decoration is a major aspect of the production of ceramic tiles. The price of

ceramic tiles is closely correlated to the quality of the decoration. The conventional

screen printing technique used for the decoration of ceramic tiles has some inherent

limitations such as screen printing directly onto weak and fragile green bodies,

resulting in significant quantities of breakages, inefficient screen printing to the edge

of the article, a high rate of wear from the abrasive ceramic particles and inadequate

screen resolution for trichromatic printing. Hence, as an efficient method, ink-jet

printing has some characteristics, i.e., computer control, less time for ceramic tiles

from design to manufacture, edge to edge printing, flexible use of images, greater

speed and industrial scale of continuous printing. Ink-jet printing has been attracted

much attention and adopted to the decoration of ceramic tiles [27–30]. In 1998, the

origin of ink-jet-based method of tile decoration was explored in Spain. Kerajet firstly

launched the practical ink-jet printer for ceramic industries in 2000 [6]. The digital

decoration of ceramic tiles took off in 2007 when the XAAR released the XAAR 1001

print head [31]. The number of ink-jet printers in operation worldwide increased

rapidly in recent 5 years (see Fig. 1) [32–35].

The inks for ink-jet printing need micro- or nano-sized pigment to avoid clogging

the nozzle and provide excellent suspension stability. The optical properties of

ceramic pigments depend on the particle size obtained, as shown in Fig. 2 [36]. The

light absorption increases with the decrease of particle size until a critical value and

finally is practically constant with size. The light scattering increases with the
decrease of particle size until a maximum approximately corresponding to half

wavelength. The optimum scattering occurs in the range of 200-400 nm as the visible

region is 400-780 nm.

In addition, the sintering process of pigments is strongly related to the specific

surface area of pigments. Some conventional pigments, such as occluded pigments,

idiochromatic pigments and allochromatic pigments were unsuitable for ink-jet

printing. The pigments used in ink-jet printing are CoAl2O4 (Cyan), Co2SiO4 (Blue), Au

(Magenta), Zn-Fe-Cr-Al spinels (Brown), CaSnSiO5:Cr (Pink), TiO2:CrSb, ZrSiO4:Pr

(Yellow), Co-Cr-Fe-Mn spinels (Black) and CoCr2O4 (Green) [36].

3 Preparation of ceramic inks

Submicron- and nano-sized pigments have a considerable market potential due

to their high surface area, which assures a higher surface coverage and a great

number of reflectance points, hence improving the scattering.

The preparation of ultra-fine (submicron-sized, commonly 400–500 nm) ceramic

pigments [16,37–39], the dispersion of ceramic pigments in the fluids and the

adjustment of physical/chemical properties of the inks are the key processes for the

production of ceramic inks. In general, the preparation of ultrafine ceramic pigments

could follow two methods, i.e., from small to big via chemical synthesis of ceramic

pigments in gas phase or liquid phase and from big to small by mechanical milling

method [40]. A high solid loading is necessary for ceramic inks to perform an

excellent color appearance in the decoration of ceramic tiles. The particles of

ultra-fine ceramic pigment have an intensive trend to aggregate each other due to

the presence of great surface energies. Hence, the preparation of highly dispersed

ceramic ink with a higher solid loading has attracted many interests in recent years.

The assessment of stability of dispersed ceramic inks, adoption of proper

stabilizer/disperser and treatment method are the key procedures, which affect the

quality of ceramic inks.

Also, various types of solvent systems for ceramic inks have been investigated.

These solvent systems include water [37], octane, hexene or isopropyl alcohol [41],

ethyl alcohol [42,43] or water/glycerol mixtures[44].

Several routes can be carried out to obtain colorants for ink-jet printing:

a) Soluble salts are solutions of metallo-organic complexes, which behave as

dyes diffusing transition elements into the vitreous phase.

b) Micron-sized pigments are conventional ceramic pigments that are ground

down to submicron-sized fractions (i.e., average diameter between 0.6 and 0.2 μm).

c) Colloidal metals are suspensions of very fine-grained crystals of noble metals

(typically below 50 nm), which affect color due to the surface plasmon resonance.

d) Nano-sized pigments are crystalline compounds, which bestow color

analogously to conventional pigments, but directly synthesized in nanoscale (usually

10-50 nm).

e) Precursors for in-situ synthesis of nano-sized pigments or colloidal metals are

solutions of metallo-organic complexes, analogue to soluble salts, which form

colored crystals directly in the ceramic matrix during firing [36,45,46].

3.1 Chemical methods

As is known, the conventional methods for the synthesis of ultra-fine particles

in liquids are the dissolution of soluble metallic salts in a liquid as pre-set formula,

precipitation or crystallization of metallic compound by adding additives,

evaporation, distillation or hydrolysis and finally the thermal treatment of obtained

precipitator or crystal to prepare ultra-fine powders. For the formulation of ceramic

inks, the sol-gel, reverse microemulsion, polyol, hydrothermal, etc., are commonly

used [47–50].

3.1.1 Sol-gel

The follow procedure of the sol-gel method is starting materials→dispersion

(hydrolysis or condensation)→sol→gelation→gel→thermal process→ultrafine

particles [51,52]. In the ceramic industry, the ceramic pigments were prepared by

sol-gel method dispersed in a solvent to obtain a ceramic ink in the late 1960s and

the early 1970s [53]. Also, the sol prepared in the sol-gel process can be used as a

ceramic ink directly to form the color in-situ on the ceramic artefact when it was

fired. Gestel et al. [54] deposited SiO2 sols with a average particle size of 9 nm onto a

γ-Al2O3 substrate by ink-jet printing and subsequent rapid thermal treatment to

produce a microporous membranes. Chouiki and Schoeftner [55] formulated an

inorganic ink-jet ink based on a SiO2 sol-gel to print on the glass for outdoor

architectural applications.

The sol-gel synthetic technique is promising in fine-tuning specific materials

properties since it can achieve a homogeneous mixing of the component cations in

an atomic scale. However, previous works on the synthesis of ceramic pigments by

the sol-gel method mainly concentrated on the hydrolysis of metal alkoxides in

organic media, which leads to some limitations for the application of sol-gel method,

i.e., a) high cost of raw metal alkoxides or salts, b) large shrinkage during processing,

c) health hazard of alcohol or non-polar organic solvents and d) extended processing

time [56]. Hence, recent work on the synthesis by the sol-gel process in aqueous

media has attracted more attentions. The aqueous processes can offer some

advantages like the use of cheaper precursors and, in many cases, more easily

handled waste products. The aqueous sol-gel processes can be classified into four

types: a) colloidal dispersions of oxide particles that are produced by another

process (i.e., a vapor phase reaction); b) colloidal dispersions of hydroxides or

hydrated oxides produced by peptizing a precipitate; c) polymerization of

hydrolyzable cations (i.e., the polynuclear cations are usually regarded as “particles”

when their “size” exceeds 1 nm); and d) precipitation of hydrated oxide or hydroxide

in the presence of an organic gelling agent (i.e., gel precipitation). The dispersions

are usually electrostatically stabilized and are capable of forming gels by increasing

concentration (loss of solvent water) or changing the pH value [57]. The aqueous

sol-gel route has been adopted to form ceramic inks for the production of functional

ceramic materials.

Aqueous sols exhibit several characteristics that make them suitable for

formulating ceramic-containing ink-jet printing inks. Firstly, the sol is a dispersion of

colloidal (or sub-micron sized) particles produced by chemical processes. Secondly,

the dispersions can be formulated to have a low viscosity at a high solid loading,

thereby achieving a high color density in the final decoration. Thirdly, the sol

droplets will form a solid gel on the substrate when some of water lost through

evaporation in drying. The gel stage could prevent the segregation of the different

ceramic-forming components in the ink (as is likely to happen when mixed salt

solutions). A major difference between the sol-gel inks and inks containing

conventional pigments is that the sol inks only contain the constituents (i.e.,

precursors) of the pigments. Consequently, the sol inks do not exhibit the final color

at the printing stage. The constituents react with each other during the subsequent

firing step and the pigments are formed in-situ at that stage [27,58–60]. Atkinson et

al. [27] demonstrated the principal steps in implementing a sol-gel process (see Fig. 3)

to synthesize the ceramic pink stain with the composition of 40.5 wt.% A12O3, 3.5 wt.%

B2O3, 37.4 wt.% ZnO and 18.6 wt.% Cr2O3. In a representative preparation, zinc

nitrate of 13.7 g and chromic nitrate of 4.87 g were firstly dissolved in an alumina sol

(i.e., aluminium chlorohydrate) of 13 cm3, and then added in a boric acid solution of

0.35 g in water of 30 cm3 to form a stable doped sol with a total oxide concentration

of 200 gdm-3. This doped sol could be oven dried to a gel powder, which was

decomposed to oxides at 700oC and further calcinated at 1020oC to produce a pink

pigment with the crystalline spinel of ZnA12O4.

Guo et al. [61] prepared the four colors (i.e., cyan, magenta, yellow, black or

CMYK) ceramic inks for ink-jet printing at a solid loading ranging from 20 vol.% to 26
vol.%. Zhou et al. [62] described a process to produce blue and black sols via the

hydrolysis of metallic salts with polyvinyl alcohol as a disperser. The similar process

was also used to prepare ceramic inks with various colors like black, yellow, red and

blue [63–67].

The functional CeO2 films can be produced by ink-jet printing with an aqueous

ink. A CeO2 precursor solution is prepared by an aqueous sol-gel route with selected

water-based starting materials such as cerium (III) nitrate hexahydrate and cerium

(III) acetate monohydrate. The CeO2 films is formed by ink-jet printing with and

without post-firing on a substrate by ink-jet printing [68–70]. The single-step process

is a potential method to produce CeO2 films, which deposit the precursor solution on

a hot substrate (< 300oC) to obtain crystalline CeO2 without further heat treatment

[70].

As a typical ceramic material, BaTiO3 ceramic inks were prepared by the sol-gel

process involving the mixing of titanium isopropoxide and barium acetate in

deionized water under continuous stirring at room temperature. Acetic acid,

acetylacetone and KOH were used to adjust the hydrolysis rate of titanium alkoxide

and the forming rate of BaTiO3. BaTiO3 powder with a median particle size of 50 nm

and a specific surface area of 68 m2/g was obtained. In order to avoid the

precipitation and satisfy the requirements of continuous ink-jet printing, a small

amount of polyacrylic acid, ammonium nitrate and polyvinylbutyral were added [71].

TiO2 as a high energy band gap semiconductor is considered to produce

functional films such as the self-cleaning, anti-fogging and hydrophilic films on the
surface of ceramic artefact. In recent years, the ink-jet printing based solutions are

used to form TiO2 films. Ohya et al. [72] evaluated the properties of the thin films

prepared from aqueous and alcoholic solutions (see Error! Reference source not found.).

Due to the high reactivity of Ti-alkoxide towards H2O, some complexing ligands are

often used as stabilizers to control the hydrolysis of Ti-alkoxide. The aqueous

precursors of TiO2 were prepared by directly mixing titanium tetraisopropoxide with

a stabilizer (i.e.,tetramethylammonium hydroxide, triethylamine, diethylamine, lactic

acid, citric acid and triethanolamine) in air at room temperature, followed by adding

an appropriate amount of water. The films from the formula of titanium

tetraisopropoxide and tetramethylammonium hydroxide showed the optimum

properties of crystallization temperature, high refractive index and film uniformity

(see Error! Reference source not found.). The films were superior to those from

commercial anatase colloidal suspension (i.e., STS-01, Ishihara Sangyo Kaisha, Ltd.

Japan). Aqueous TiO2 precursor solutions, which were prepared with tetrabutyl

orthotitanate as Ti source and citric acid or triethanolamine as stabilizing agents,

were ink-jet printed on a glass substrate to form the photocatalytically active TiO2

thin films via heat treatment. The film based on triethanolamine exhibited a smaller

grain size and a lower surface roughness with comparison to the citric acid based

layer [73]. In addition, the complexing stabilizer is an option to optimize the

synthesis of precursor solutions. The interaction effect of a complexing stabilizer

consisting of ethylenediaminetetraacetic acid and triethanolamine on the synthesis

of TiO2 precursor solution for ink-jet printing was investigated [74]. Meanwhile, the
stabilization of different metal ions in aqueous precursors were discussed, such as

citric acid stabilized Ce4+ and Bi3+ [68,75–78], tartaric acid/nitrilo-triacetic

acid/Triethanolamine stabilized Y-Ba-Cu-O system [79–81], monoethanolamine

stabilized Zn2+[82], polyethylene glycol/polyethylene glycol monoalkyl

ether/branched diol/polyethylene glycol dialkyl ether/monohydric alcohol stabilized

Al3+[83].

3.1.2 Reverse microemulsions

Microemulsions are clear, thermodynamically stable, isotropic liquid mixtures

of oil, water and surfactant, frequently in combination with a co-surfactant. The

aqueous phase may contain salt(s) and/or other ingredients, and the oil phase may

be a complex mixture of different hydrocarbons and olefins. The three basic types of

microemulsions are direct (oil dispersed in water, o/w), reversed (water dispersed in

oil, w/o) and bi-continuous. The characteristic properties of microemulsions like high

thermodynamic stability, ultralow interfacial tension and large interfacial area can

make them a competent vehicle for ink-jet inks. The microemulsion is spontaneously

formed by proper surfactant, solvent and co-solvent. The initial microemulsion is

thermodynamically stable, with the droplet size of 10-20 nm, which is excellent for

storage stability and prevention of print head malfunctions. The use of

microemulsions as a vehicle for ink-jet inks was reported in 1991 [84]. The important

properties of microemulsion, such as particle size, are governed mainly by the

diameter of the water cores, which are related to the water-surfacant molar ratio
(R=[H2O]/[surfactant]) [85,86].

The oil-in-water microemulsions require a water-insoluble organic material as a

colorant [87], such as dyes [88], which means that the inorganic pigments for

ceramic decoration cannot be applied in this system. Therefore, a so-called reverse

microemulsion is developed for inorganic materials. The water is spontaneously

suspended into the continuous oil matrix in nano-scale. The water particles provide

reaction spaces for the formation of ceramic nanoparticles. However, a reverse

microemulsion system usually has a low water-dissolving amount, which is not

enough to prepare a ceramic ink with a required solid content. Hence, the increase

of water-dissolving amount is one of the most important problems before the

reverse microemulsion are used to form ceramic inks practically. The choice of a

proper reverse microemulsion system, the use of co-surfactant and the optimization

of preparation conditions are the efficient paths to solve this problem [89,90].

Gemini surfactants are amphiphiles composed of two identical hydrophobes linked

to two head groups with a spacer moiety. Magdassi et al. [87,91] evaluated an

effective Gemini surfacant, i.e., didodecyldiphenylether disulfonate (C12-DADS).

They found that the C12-DADS leads to the formation of either oil-in-water or

water-in-oil microemulsions.

Guo et al. [89] formed a reverse microemulsion with octyl phenol ethylene

oxide condensate (TX-100) as an emulsifier, n-hexanol as a co-emulsifier and

cyclohexane as an oil phase to prepare ZrO2 ceramic ink. The optimized composition

for the maximum water content of the system above was 19.1% Triton X-100/12.8%
n-hexanol/23.7% cyclohexane/44.4% water in mass determined by its quasi-ternary

phase diagram. ZrO2 ceramic ink with superior stability, dispersivity and

homogeneity was formulated by mixing the two reverse microemulsions uniformly,

which were obtained by the replacement of water in the system with equivalent

volume of zirconium oxychloride solution and ammonia solution, respectively.

Monnoyer et al. [92] synthesized AgBr nanoparticles in a

AOT—n-heptane—water system. AOT or Aerosol OT is the dioctyl sodium

sulfosuccinate, which produces a surfactant film to stabilize the water cores. The size

of AgBr nanoparticles synthesized ranges from 50 to 200 Å, which can be adjusted by

choosing both the concentrations of precursor salts and the size of the water cores.

Ag2Se and AgCl nanoparticles could be produced by the similar method [93,94].

Jovaní et al. [95] prepared a ceramic pigment with a nominal composition of

Ti0.97Cr0.015Sb0.015O2 by a microemulsion mediated solvothermal method at 180 oC.

The size, shape, color and electrostatic stability of these particles make them

potential candidates to be applied in glazes or inkjet printers as orange ceramic

pigments.

3.1.3 Polyol

The polyol method is a well-known synthesis technique to prepare fine particles

of metal or metal oxide. The fine particles are obtained by heating a solution formed

by adding a precursor into a polyol, which has a high boiling point, at a temperature

below boiling point under atmospheric pressure. Some inorganic pigments, such as
CoAl2O4 (blue), Cr2O3 (dark green), ZnCo2O4 (green), (Ti0.85Ni0.05Nb0.10)O2 (yellow),

α-Fe2O3 (red) and Cu(Cr, Fe)O4 (black) are widely applied in paints, building materials,

plastics, enamel, and ceramics [96]. In conventional methods, the pigment materials

are prepared at > 500 oC and have a grain size larger than 500 nm. A d-d transition or

host-lattice absorption is the origin of color, the body color of the pigments

mentioned above is closely related to the degree of material crystallinity. However,

for the pigments applied in ceramic inks, a smaller particle size (< 500 nm) and a

higher crystallinity of materials are required. The polyol method can synthesize

mono-dispersed nano-sized pigments with a superior color quality at a lower

temperature. In the polyol method, the polyol with a high boiling point (such as

diethylene glycol ，DEG) acts both as a solvent and as a reducing agent, which makes
the solution possible to work at high temperatures and to complex the particles

being formed, thus preventing their growth [97–101]. Some materials synthesized by

the polyol method are suitable to form ceramic ink-jet inks with the solid content of

20 wt.% to ensure the optimal color performance due to the high stability offered by

polyol suspensions [36].

Baldi et al. [99] obtained the nanoparticles of ceramic colorants with the sizes of

5-600 nm by the polyol method. Ceramic inks can be prepared via the in-situ

dispersion of the particles in diethylene glycol, ethylene glycol or polyethylene glycol.

The polyol method is suitable to synthesize the ceramic colorants defined as

MIIMIII2O4, where MII is chosen in the group consisting of FeII, ZnII, CoII, NiII, MnII, and

MIII is chosen in the group consisting of FeIII, AlIII, CrIII, MnIII, such as CoAl2O4, Ti(Sb,
Cr)O2, (Zr, Pr)SiO4, (Zr, V)SiO4, (AlCr)2O3, (Al, Cr)MO3(M = Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho,

Er, Tm, Yb), CaSn1-xCrxSiO5, Ti(Sb, Ni)O2, (Zr, V)O2, (Sn, V)O2, Sn1-xCrxO3-x/2 (where x is

comprised between 0.01 and 0.1) , Au0, Ag0, Cu0. Merikhi et al. [102] prepared

CoAl2O4 particles with the sizes of 50-200 nm controlled by adjusting the

concentration of the components (i.e., metal precursor, water). The solid loading of

suspensions in diethylene glycol is 10 wt.%. The surface of the oxide particles is

complexed by diethylene glycol, leading to a stabilized solution against aggregation,

even mixed with water. Gardini et al. [103,104] developed the CMYK ceramic inks for

the decoration of ceramic articles in glycol by the polyol process. Error! Reference

source not found. shows the color appearance of the inks. Dondi et al. [36] also

prepared a series of ink-jet inks with various colors like black (CoFe2O4), blue

(CoAl2O4), yellow (Ti(Cr, Sb)O2), and magenta (Au or Cu) by the polyol method.

Izu et al. [105,106] developed a polyol method to prepare sols of spherical ceria

nanoparticles for ink-jet printing ink with polyvinyl pyrrolidone (PVP) and cerium

nitrate Ce(NO3)3·6H2O as the raw materials. The results showed that the spherical

nanoparticles had a core-shell-type ceria/polymer structure with the sizes of 50-120

nm, which could be adjusted by changing the molecular weight of PVP. The spherical

core-shell type nanoparticles have a superior dispersibility in water or alcohol [107].

The shell around nanoparticles formed by polyol is considered as the major factor to

control the growth of nanoparticles, i.e., size of particles. The formation mechanism

of nanoparticles is considered to be that the primary particles of cerium oxide

nucleate and aggregate to grow the secondary particles. Because the space of the
nucleation is several nanometers, PVP has to be excluded in order to increase the

size of the secondary particles to tens of nanometers. Although a small force is

needed for the exclusion of PVP of low molecular weight, a larger force is needed in

the case of high molecular weight. In the case of high molecular weight, it is

considered that the growth rate of the secondary particles is low due to the larger

force, and the growth stops early due to the formation of PVP layer around the

secondary particles. This may be the reason why the particle size decreases with

increasing the molecular weight of PVP.

3.1.4 Hydrothermal

Hydrothermal processing routes to synthesize ceramic powders involve heating

reactants, often metal salts, oxide, hydroxide or metal powder as a solution or

suspension in a liquid usually, but not necessarily, water at elevated temperature

and pressure in an autoclave. Hydrothermal synthesis can be defined as a method of

synthesis of single crystals that depends on the solubility of minerals in hot water

under a high pressure [108]. The advantages of the hydrothermal method include:

a) The nucleation and particle growth in the hydrothermal process can result in

submicron-sized oxide, non-oxide or metallic particles with controlled shape.

b) The hydrothermal method is suitable for the growth of large good-quality

crystals.

c) The hydrothermal process can be performed at a relative low temperature,

usually 100-200oC, and some impure reactants are acceptable. The subsequent
calcination at a higher temperature is not necessary, which leads to the growth of

grain size and contamination. For instance, Cd(SxSe1-x) as a scarlet ceramic pigment

decomposes at 800°C and needs to be coated by ZrSiO4 before it is used for the

production of ceramic tiles. Compared to the solid reaction and sol-gel methods,

hydrothermal method can produce ZrSiO4 at a low temperature without subsequent

calcination. Hence, hydrothermal method is an efficient route to synthesize ZrSiO4

encapsulated Cd(SxSe1-x) ceramic pigment.

Based on the hydrothermal method, the microwave heating, which directly

heats the solutions immediately, is introduced to prepare mono-dispersive

nanoparticles and accelerate the reaction. The α-Fe2O3 (i.e., hematite) powder is

often used in ceramic industry as a red pigment. However, it is difficult to obtain

nanoparticles of α-Fe2O3 ( ＜100 nm) by a conventional hydrothermal method.

Katsuki and Komarneni [109–112] developed a microwave-hydrothermal method to

prepare nanoparticles of α-Fe2O3. The mono-dispersive nanophase α-Fe2O3

(hematite) was synthesized via microwave-hydrothermal and conventional

hydrothermal reactions using 0.018M FeCl3·6H2O and 0.01M HCl solutions at

100-160°C. The spherical nanoparticles of α-Fe2O3 with the sizes of 50-100 nm were

obtained with β-FeOOH crystals after 13 h via the conventional hydrothermal

reaction. The α-Fe2O3, particles with the sizes of 100-180 nm were preferentially

formed after heat treatment at 100°C for 24 h and the yield reached 68.9%. The yield

of 77.8% was obtained after heat treatment at 100°C for 48 h. However,

mono-dispersive particles of α-Fe2O3 with the size of 31 nm were formed without

any β-FeOOH in microwave-hydrothermal reaction at 100°C for 2 h. The yields of

α-Fe2O3 particles at 100°C via the microwave-hydrothermal reaction were 18.9% for

2 h and 56.8% for 8 h, respectively. The mono-dispersive and uniform α-Fe2O3

particles with the sizes of 50-60 nm suitable for a ceramic pigment were formed at

120-160°C via the microwave-hydrothermal reactions. As a rapid and efficient

method, the microwave-hydrothermal reaction can be also used to prepare the

aqueous suspensions of TiO2 particles [74,113] and CoAl2O4 particles [114] for ink-jet

printing.

Kim et al. [115] prepared well-dispersed nanoparticles of CoAl2O4 for ink-jet

printing by a hydrothermal process with ultrasonic irradiation. The introduction of

ultrasonic irradiation to the hydrothermal process favors the synthesis of the

nano-sized pigment of CoAl2O4 with a better crystallinity. The ultrasonic-assisted

powder has a uniform square morphology and a narrower size distribution with an

average particle size of <100 nm. However, the microscopic morphology of CoAl2O4

pigment that is mechanically stirred implies an irregular structure with a wider size

distribution. The cavitation effect induced by ultrasonic irradiation contributes to

the complete blending of precursors and produces the nanopowder of CoAl2O4 with

the narrower size distribution, giving a better color appearance.

3.1.5 Others

Kosmala et al. [116,117] synthesized a water-based inks with Ag nanoparticles,

which could eliminate the environmental problem like volatile organic compounds.
Silver nitrate was used as a precursor with dioctyl sodium sulfosucinate (AOT) as a

capping agent. N2H4OH and NaOH were added to complete the precipitation of Ag

nanoparticles. The synthesized Ag nanoparticles were dispersed in water with

Pluronic F127 as a disperser to form a Ag inks. A technique named high intensity

frequency ultrasound (HIFU) was applied to enhance the dispersion and stability of

the inks with a solid loading up to 45 wt.% by breaking and de-aggregating the

micron-sized particles into the nano-sized ones and effectively forming the

nano-suspensions. Compared to the conventional ultrasonic agitation and mechanic

milling methods, the HIFU has some advanced aspects, i.e., (1) the high amplitudes

(up to 108 Pa) and frequency (∼106 Hz) to induce the non-linear propagation effects;

(2) since the frequency of ultrasound is increased from∼104 Hz to ∼106 Hz, the

threshold value of intensive micron-scale transient cavitations are significantly

increased. Therefore, the immense temperature and pressure and the extraordinary

heating and cooling rates generated by cavitation bubble collapse could be alleviated.

There is no distinct temperature increase at all; and (3) it avoids the possible

contamination to the fluid due to bead wear during prolonged milling process. The

process of mechanic milling to disperse Ag nanoparticles in water needs a few tens

of hours, in some cases, even days. However, the HIFU process only needs tens of

minutes. Wang et al. [118] prepared ferroelectric PZT particles with the assistance of

HIFU due to the features of HIFU mentioned above. The typical average particle size

of PZT particles prepared by a hydrothermal method is between 500 and 1000 nm.

The average size of the particles is reduced to as small as 10-20 nm when the HIFU is
used.

Peymannia et al. [50] prepared different types of nano-sized pigments of

CoAl2O4 with the average particle size of 45 nm by controlling the concentration of

cetyltrimethylammonium bromide (CTAB) and polyvinylpyrrolidone (PVP) as double

capping agents in a co-precipitation process with cobalt nitrate [Co (NO3)3·9H2O] and

aluminum nitrate [Al(NO3)3·9H2O] as starting materials. The synthesized

nanoparticles of CoAl2O4 were properly dispersed by an itaconic acid-co-acrylic acid

dispersant in de-ionized water, diethylene glycol (DEG) and ethanol uniformly to

form the ink with a solid loading of 8 wt%. The particle size of CoAl2O4 pigment is

correlated to the concentrations of CTAB and PVP. PVP contains hydrophilic polar

groups (i.e., O and N), which interact with Co2+and Al3+ ions on N or C=O with their

lone electron pairs. In addition, steric effect of the PVP would restrict the growth of

the nanoparticles and thus inhibit the agglomeration of the nanoparticles. As a

cationic surfactant, the CTAB easily coordinates with the nanoparticles of CoAl2O4 by

ammonium nitrogen. The CTAB also forms a similar double-layer structure around

the nanoparticles of CoAl2O4, which separate the nanoparticles of CoAl2O4 by

electrostatic forces and steric effect. It is the coupling interaction between the two

surfactants that makes the nanoparticles well suspended in the solution, thus

preventing the further aggregation of the nanoparticles of CoAl2O4.

Wagata et al. [46] prepared a precursor solution with barium isopropoxide,

titanium tetra isopropoxide and dehydrated ethanol as starting materials to

fabricate BaTiO3 microdots by ink-jet printing. To prevent the precipitation of

starting materials by hydrolysis, an amino acid, i.e., L-proline, which can efficiently

form a complex with various metal ions, was used to stabilize Ba and Ti species.

Blosi et al. [119–121] developed a simple and eco-friendly microwave-assisted

route for producing gold, silver and Au-Ag core-shell structures in the form of stable

nano-suspensions by glucose reduction in water at a low temperature and an

ambient pressure. Au/Ag nano-particles were prepared by a two-step method to

obtain the core-shell nanostructure (see Fig. 4).

Au-core and Ag-core sols, exploited as seeds, were obtained separately

throughout the reduction of HAuCl4 or AgNO3 by D(+) glucose in alkaline water.

PVP-coated metal seeds were synthesized by microwave heating. The typical

procedure used to synthesize gold or silver seeds requires a water solution

containing the chelating agent (i.e., polyvinylpyrrolidone), the reducing agent (i.e.,

D(+) glucose) and the required amount of NaOH in order to maintain a pH value of 6

(for Ag) and of 9 (for Au). The particle size was controlled by the careful optimization

of the solution pH value, the chelating agent to metal ratio and the glucose to metal

ratio. Moreover, this method was applied to the microwave-assisted synthesis of

Pr–ZrSiO4, V–ZrSiO4 and Cr–YAlO3 ceramic pigments [122].

3.2 Mechanical grinding

Besides the chemical methods, a possible approach is to process the

micron-sized powder using a conventional synthesis method and subsequent

mechanical grinding for the reduction of the particle size to the required dimensions
[39,123]. The grinding method is comprehensively applied in the preparation of

ceramic inks to enhance the dispersion of ceramic particles obtained by chemical

method in a carrier fluid [15,124–126]. In addition, the mechanical grinding is

promising in the production of ceramic inks since the preparation of ultrafine

particles and the adjustment of the properties of suspension, which is important to

perform the ink-jet printing, can be completed in the same process.

Many attempts were carried out to discuss the possibility of the preparation of

ceramic inks by mechanic grinding method, such as inks containing TiO2

[39,49,127–129], ZrO2 [15,20,130–138], Pb(Zr0.53Ti0.47)O3 (PZT) [139], Ag [140–142],

BaTiO3 [21,71], Al2O3 [143–146], Si3N4 [38,147]. Kuscer et al. [39] present a general

protocol for processing cost-beneficial, environmentally benign aqueous suspensions

suitable for piezoelectric ink-jet printing. The formulation of a highly stable, colloidal,

water-based suspension containing TiO2 particles of < 570 nm prepared by a grinding

process was discussed. The surface tension and the viscosity of the suspension were

adjusted by the addition of a small amount of the appropriate non-ionic amphiphiles

and glycerol. The correlations of milling time and pH value to the particle size and

dispersion stability of the suspension were evaluated (see Fig. 5 and Fig. 6). Kim et al.

[49] investigated the effect of molecular weight of dispersant on the dispersion

stability of an aqueous TiO2 suspension. Four polymer dispersants were the random

copolymer of methacrylic acid and n-butyl acrylate with the molecular weights of

6300, 8300, 9400 and 20000, respectively. A better stability of TiO2 suspension was

observed by using the greater molecular weight polymers. They also proposed the
effect of molecular weight on the suspension stability due to the steric and

electrostatic effects.

As a solid freeform fabrication technique, the ink-jet printing can easily

assemble the shaped ceramic components. However, ceramic inks with a higher solid

loading are critical to prepare the ceramic articles with the superior properties. Özkol

et al. [132–136] dispersed zirconia particles into an aqueous medium using a

commercial carboxylic acid-based dispersant by stirred bead grinding to form ceramic

inks with the solid loading ranging from 20 to 27 vol.%. The printability of inks and

the mechanical properties of zirconia articles were evaluated. A similar work was

carried out [137,138] to form a zirconia ceramic ink with the solid loading of 30 vol. %

in a system consisting of butyl acetate (solvent) and a commercial oligomeric

dispersant. The sediment packing efficiency was used as an indication of the degree

of dispersion. Also, some other inks with a great solid content such as the mixture of

Si3N4 and MoSi2 powders [147], the mixture of Si3N4 and yttrium–aluminium–garnet

powders [38], Al2O3 [145], BaTiO3 [21] were investigated.

Mechanical grinding is a complicated process. For effective grinding, the

property of ceramic powder, the particle size of ceramic powder before/after

grinding, the type and amount of dispersant, the parameters of grinding process (i.e.,

mill type, milling time, circumferential speed, size of grinding beads, etc.), the pH

value and solid loading of suspension, etc. should be considered in the process.

Noshchenko et al. [148] dispersed/milled the micron-sized Pb (Zr0.53Ti0.47)O3 (PZT)

particles in water at pH 3 and pH 10 with the ammonium polyacrylate (PAANH4) as a

dispersant in a colloidal mill. The results revealed that PAANH4 has different

dispersing mechanisms at different pH values. In acid medium, the PAANH4 is in the

coil configuration, which means the dispersion behavior is mainly controlled by

electrostatic stabilization. The PZT particles aggregated after prolonged milling. The

dispersion stability of the PZT particles was improved in alkaline medium, where the

PAANH4 is dissociated and is in the tail configuration. The electrostatic and steric

stabilizations of the PZT particles both are efficient. Hence, the well-dispersed PZT

particles with the particle size of < 580 nm could be obtained in alkaline medium.

Chartier et al. [149] proved the possible degradation of dispersant in grinding process,

decreasing the grinding efficiency. The degradation of poly(methacrylic acid)

(PMAA-NH3) was assessed during wet milling of a calcined α-alumina. The

degradation of dispersant could occur since 1) the decrease of the charge by

dehydration induced a small aggregation of alumina particles and the rheological

behavior of the slurry is not affected; 2) the complete neutralization of the dispersant

by the formation of monodentate COOX groups, leading to the desorption of the

polymer from the alumina surface, involved a significant aggregation.

Since the grinding method needs a high energy input, especially for the

preparation of nanoparticles, some issues must be considered to perform a grinding

process to prepare ceramic inks. It is difficult to control the particle size distribution

in grinding. Furthermore, grinding introduces contamination and damages the crystal

perfection, which will affect the color appearance [150,151]. The ground particles

have irregular shapes, leading to the poor suspension rheology and abrasion to the
nozzle of ink-jet printer somehow.

4 Challenges for future development

a) The color performance of ceramic inks for ink-jet printing cannot satisfy the

requirements of ceramic industry so far. The ingredients of ceramic pigments

have to be developed to improve the color appearance of ceramic inks.

b) The improvement of the color appearance of ceramic inks is the use of coarser

ceramic pigment particles (i.e., micron-sized). Ferro Corporation (USA) already

developed the novel inks with 10 colors that deliver greater color intensity, larger

particle size (up to 3 microns), and third-firing decoration. However, the use of

coarser pigment particles has a negative effect on the printability of inks. This

aspect should be further developed.

c) From the viewpoint of environmental protection, there is an urgent need to

develop environmentally friendly alternative chemical protocols to reduce the

use of hazardous, expensive, and toxic materials. Hence, the preparation and

application of water-based ceramic inks are attracting interests in the existing

industry [38,47,48,152,153]. For the decoration of ceramic tiles, the green body,

the kiln, etc. should be adjusted to be suitable for the ink-jet printing of

water-based inks.

d) It is necessary to sinter ceramic tiles at a high temperature. The heat treatment

will affect the color performance of temperature-sensitive ceramic pigments. A

 novel method called ink-jet reaction could be possible to solve this problem. The

ink-jet reaction is proved to be an efficient route to prepare ceramic film by

ink-jet printing an aqueous precursor solution on the substrate at room

temperature or moderate temperatures without further heat treatments

[154,155].

e) The ceramic manufacturers require a better decoration performance based on

the ink-jet printing. Hence, some novel techniques have been developing or

already developed, such as printing of dry powders, printing of glaze (digital

glazing) [35], the inks of glisten glaze, the inks of matt glaze. Meanwhile, some

functional inks are developed, i.e., the allochroic inks under different light

sources [156–158], the ink that can release the anions, the photocatalytic inks

[159], etc., to provide the superior functions for ceramic tiles.

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Caption of figures

Fig. 1 Ink-jet printers worldwide [32–35].

Fig. 2 Optical properties (absorption and scattering of visible light) as a function of

particle size and specific surface area of pigments [36].

Fig. 3 Example of a sol-gel pigment composition that can be applied to decorate

ceramics in different ways [57].

Fig. 4 Flow chart of synthesis of bimetallic nano-particles [120].

Fig. 5 The mean volume particle size dv50 of TiO2 as a function of milling time for

suspensions containing 5 vol.% of TiO2 with initial pH values of 7.5 and 11 [39].

Fig. 6 ζ-potential of aqueous TiO2 suspension as a function of pH value [39].

Fig. 1

Fig. 2

Fig. 3
Fig. 4

Fig. 5

Fig. 6
Table 1 Properties of the TiO2 thin films prepared from aqueous and alcoholic solutions refined
based on [72].

Crystallization Refractive Film

Solvent Stabilizer Ra
temperature (oC) indexb uniformity
Tetramethylammonium
Water 0.4 350 2.40 Excellentc
hydroxide
Diethylamine 0.4 600 2.33 Fair
Triethylamine 0.5 600 2.34 Fair
Lactic acid 1 400d 2.21 Poor
Lactic acid-NH3 1 400d 2.30 Good
Citric acid-NH3 1 500 2.33 Good
Triethanolamine 1 500 2.33 Fair
HNO3 - - 1.65 Poor
2-propanol Diethanolamine 1 500 2.30 Excellent
Triethanolamine 1 500 2.33 Excellent
Acetoin 2 400 2.12 Good
Acac 2 400 2.08 Good
a
R =[Stabilizer]/[Ti], molar ratio.
b
For the films heat-treated at 600oC.
c
In the presence of sugar.
d
Brown-colored film.
Table 2 Colourimetric properties of nano-inks applied on ceramic tiles.
Nano-ink
Property Unit Cyan Magenta Yellow Black
(Co1−xO) (Au0) (Ti1−x−ySbxCryO2) (CoFe2O4)
L* 52.4 ± 0.8 37.0 ± 1.1 79.9 ± 2.1 14.2 ± 0.9
Colour (CIE-Lab) in bright
a* +10.3±1.0 43.4±0.2 1.8±1.2 +3.1±0.1
glaze
b* −35.1±2.0 4.4±1.1 47.2±1.8 −6.4±1.0
L* 63.3±1.1 56.1±0.5 80.7±0.9 35.6±0.8
Colour (CIE-Lab) in porcelain
a* −3.3±0.1 17.7±0.3 1.8±0.7 +0.4±0.1
stoneware
b* −11.9±0.7 2.5±0.1 35.5±2.3 +0.8±0.1