Porcelain

Porcelain
Porcelain and vitreous enamel is a material obtained by melting or fritting a mixture
of inorganic materials.

From: Reference Module in Materials Science and Materials Engineering, 2016

Related terms:

Al2O3, Sintering, Glass Ceramics, Aluminum Oxide, Zirconia, Cobalt, Feldspar,

Cermets, Glaze

View all Topics

INTRODUCTION
 INTRODUCTION
George Wypych, inGeorge
Handbook
Wypych,
of Surface
in Handbook
Improvement
of Surface
and Improvement
Modification, and
2018Modification, 2018

Porcelain was mostPorcelain

likely thewas
firstmost
multilayer
likely the
material
first multilayer
created tomaterial
differentiate
created
prop-
to differentiate prop-
erties of the surface
erties
fromofthe
thebulk.
surface
Glazed
fromporcelain
the bulk.was
Glazed
invented
porcelain
in China
was during
invented in China during
Sui dynasty (581-618SuiAD).
dynasty
The (581-618
external surface
AD). Theof external
a porcelain
surface
baseofwas
a porcelain
coated with
base was coated with
a vitreous glaze anda vitreous
baked inglaze
a kilnand
at 1200°C.
baked inThis
a kiln
resulted
at 1200°C.
in a very
Thislow
resulted
waterin a very low water
absorption coefficientabsorption
(below 0.004)
coefficient
and extremely
(below 0.004)
hardandsurface.
extremely
The ancient
hard surface.
GreeksThe ancient Greeks
painted their potteries
painted
as early
theiraspotteries
in 11th ascentury
early as
BC,inbut
11th
only
century
for the
BC,
decorative
but only for the decorative
purposes. The Egyptians
purposes.
hadThe
done Egyptians
it much earlier
had donearound
it much
3300earlier
BC. around 3300 BC.

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History of
History
Sintering
of Sintering
Randall M. German,
Randall
in Sintering:
M. German,
from in
Empirical
Sintering:
Observations
from Empirical
to Scientific
Observations
Princi-to Scientific Princi-
ples, 2014 ples, 2014

Porcelain Porcelain
Porcelain was a valuable
Porcelain
sintered
was aproduct
valuablethat
sintered
arose product
first in China.
that arose
A keyfirst
to porcelain
in China. A key to porcelain
production is in attaining
production
a high
is in
firing
attaining
temperature.
a high firing
Progressive
temperature.
advances
Progressive
in kiln advances in kiln
design generated higher
designfiring
generated
temperatures
higher firing
and greater
temperatures
strength.
andAccordingly,
greater strength. Accordingly,
porcelain firing advanced
porcelain
to firing
give leak-free
advanced structures
to give leak-free
by aboutstructures
1600 BC.by about 1600 BC.

Firing temperaturesFiring
of 1300°C
temperatures
(1573 K)ofallowed
1300°Cquartz
(1573 K)
to partially
allowed dissolve
quartz tointo
partially
sili- dissolve into sili-
cate glass which then
cate
gained
glass which
strength
then
bygained
crystal precipitation
strength by crystal
on cooling.
precipitation
The success
on cooling. The success
of Chinese porcelain
of Chinese
was widely
porcelain
recognized,
was widely
and became
recognized,
a target
andforbecame
considerable
a target for considerable
trade. An example trade.
of the An
highly
example
valued
ofTsing
the highly
dynastyvalued
porcelain
Tsing isdynasty
shownporcelain
in Figureis shown in Figure
2.3. 2.3.
Figure 2.3. A TsingFigure
dish fabricated
2.3. A Tsing
with
dish
a high
fabricated
temperature
with a sintering
high temperature
process. sintering process.
Figure 2.5. Early Chinese
Figure 2.5.
porcelain
Early Chinese
productionporcelain
excelledproduction
in reaching excelled
high sintering
in reaching high sintering
temperatures by usetemperatures
of sloped dragon
by usekiln
of sloped
design,dragon
sketchedkilnindesign,
this early
sketched
illustration.
in this early illustration.
Figure 2.6. European
Figure
porcelain
2.6. European
eventually
porcelain
found composition
eventually found
formulations
composition
and formulations and
sintering techniques
sintering
capabletechniques
of formingcapable
high value
of forming
products,
high
initially
valuenear
products,
Dresden.
initially near Dresden.
veneers. Sometimes the chipping is small and does not affect the proximal contact
area with the adjacent teeth or change the contour of the teeth. In this case, the
dental restoration could still perform as normal and did not fail. In another instance,
however, the restoration can ultimately fail and need to be taken out and replaced,
especially when the chipping damage of the proximal margin ridge results in the
loss of the normal contact area with adjacent teeth.
 veneers. Sometimes the chipping is small and does not affect the proximal contact
area with the adjacent teeth or change the contour of the teeth. In this case, the
dental restoration could still perform as normal and did not fail. In another instance,
however, the restoration can ultimately fail and need to be taken out and replaced,
especially when the chipping damage of the proximal margin ridge results in the
loss of the normal contact area with adjacent teeth.

When a crack penetrates

When athe crack
porcelain
penetrates
layerthetowards
porcelain
the porcelain–core
layer towards the interface
porcelain–core
it interface it
is often deflected along
is oftenthisdeflected
interface.along
The relatively
this interface.
weakThebond relatively
at the porcelain–core
weak bond at the porcelain–core
interface comparedinterface
to the mechanically
compared tostrong the mechanically
inner core material
strong inner
results
corein material
partial results in partial
porcelain delamination.
porcelainPorcelain
delamination.
chippingPorcelain
is observed chipping
in association
is observed
withinthicker
association with thicker
porcelain layers, while
porcelain
delamination
layers, while
is often
delamination
a result associated
is often awith
result
thinner
associated
porce-with thinner porce-
lains. This behaviorlains.
is comparable
This behavior
to theis situation
comparable observed
to the situation
by finite element
observedanalysis
by finite element analysis
(FEA) in bending test
(FEA) simulations,
in bendingwheretest simulations,
it is clearly predicted
where it isfrom
clearly
thepredicted
material’sfrom the material’s
intrinsic properties.intrinsic
The interfacial
properties.
delamination
The interfacialhas been
delamination
ascribed either
has been
to the
ascribed
large either to the large
mismatch of the fracture
mismatch toughness
of the fracture
alone, or toughness
to both thealone,
fracture
or totoughness
both the fracture
and toughness and
elastic modulus mismatches.
elastic modulus In anmismatches.
FEA simulation, In an
theFEA
differences
simulation,of the
the elastic
differences of the elastic
modulus are dominantmodulus and areto adominant
lesser extent andaffected
to a lesser
by the
extent
fracture
affectedtoughness.
by the fracture toughness.
Yet, the effect of fracture
Yet, thetoughness
effect of fracture
is actingtoughness
indirectly,isasacting
bendingindirectly,
strength as is
bending strength is
proportional to toughness
proportionaland relates
to toughness
also to andthe critical
relates defect
also tosize.
the critical
The FEA defect size. The FEA
simulation reveals simulation
that the frequent
revealsinterfacial
that the frequent
delamination
interfacial
observed
delamination
in zirconiaobserved in zirconia
bi-layer compositesbi-layer
comparedcomposites
to aluminacompared
compositesto alumina
is initiated
composites
by higheris initiated
shear by higher shear
stresses building upstresses
along building
the zirconia
up along
interfacethedue
zirconia
to theinterface
mechanical
due property
to the mechanical property
differences of thesedifferences
two constitutional
of these twoceramic
constitutional
components. ceramic
This components.
suggests that Thisthe suggests that the
delamination observed
delamination
for zirconiaobserved
copings formight
zirconia
be reduced
copings might
by increasing
be reduced
the by increasing the
bending strength of bending
the veneer
strength
porcelain.
of theTheveneer
FEA porcelain.
simulations Thediscussed
FEA simulations
above were discussed above were
carried out under the
carried
condition
out under
of one
theloading
condition
cycle
ofand
onethe
loading
resultscycle
are and
illustrated
the results
in are illustrated in
Figure 5.6. BearingFigure
in mind 5.6.that
Bearing
interfacial
in mind
delamination
that interfacial
startsdelamination
well before any starts
crack
well before any crack
propagates through propagates
the zirconiathrough
coping,the
one
zirconia
can understand
coping, onethatcanveneer
understand
flakingthat veneer flaking
may occur and thatmayno critical
occur anddamage
that no
to critical
the zirconia
damage
coretoitself
the zirconia
has taken core
place.
itself has taken place.
This is consistent with
This the
is consistent
fact that veneer
with theflaking
fact that
of zirconia
veneer flaking
crowns of andzirconia
bridgescrowns
is and bridges is
frequently observedfrequently
in the clinic.
observed in the clinic.
Figure 5.6. The optical microscope views of the surface perpendicular to the fracture
surface of a zirconia (a) and an alumina (b) bi-layer specimen after a 3-point bending
test in comparison with the FEA simulated fracture of zirconia (c), and alumina (d).
The observed experimental fracture modes agree with the FEA simulations. In bend-
ing of zirconia bi-layer composites, severe interfacial delamination was observed (a).
The ‘a’ arrows in this image indicate pieces of veneer porcelain completely peeled
away from the zirconia core; ‘b’ arrows indicate the location of fracture surfaces of the
specimen; arrow ‘c’ indicates the zirconia core surface after interfacial delamination;
and arrow ‘d’ indicates the veneer porcelain remaining on core interface. In the
case of alumina bi-layer composites it is obvious that interfacial delamination was
very low, see image (b). The ‘a’ and ‘b’ arrows indicate the location of fracture
surfaces; arrow ‘c’ indicates a tiny delamination zone; and arrow ‘d’ indicates the
location of the veneer/core interface.(From Liu YH, Feng HL, Bao YW, Qiu Y, Xing N,
Shen ZJ. Fracture and interfacial delamination origins of bilayer ceramic composites
for dental restorations. J Euro Ceram Soc, 2010;30(6):1927-1305. Reproduced with
permission of Elsevier Limited.)
 Figure 5.6. The optical microscope views of the surface perpendicular to the fracture
surface of a zirconia (a) and an alumina (b) bi-layer specimen after a 3-point bending
test in comparison with the FEA simulated fracture of zirconia (c), and alumina (d).
The observed experimental fracture modes agree with the FEA simulations. In bend-
ing of zirconia bi-layer composites, severe interfacial delamination was observed (a).
The ‘a’ arrows in this image indicate pieces of veneer porcelain completely peeled
away from the zirconia core; ‘b’ arrows indicate the location of fracture surfaces of the
specimen; arrow ‘c’ indicates the zirconia core surface after interfacial delamination;
and arrow ‘d’ indicates the veneer porcelain remaining on core interface. In the
case of alumina bi-layer composites it is obvious that interfacial delamination was
very low, see image (b). The ‘a’ and ‘b’ arrows indicate the location of fracture
surfaces; arrow ‘c’ indicates a tiny delamination zone; and arrow ‘d’ indicates the
location of the veneer/core interface.(From Liu YH, Feng HL, Bao YW, Qiu Y, Xing N,
Shen ZJ. Fracture and interfacial delamination origins of bilayer ceramic composites
for dental restorations. J Euro Ceram Soc, 2010;30(6):1927-1305. Reproduced with
permission of Elsevier Limited.)

Failed ceramic crownsFailed

have
ceramic
been observed
crowns havein the
beenclinic
observed
with porcelain
in the clinic
chipping-off
with porcelain
t chipping-off t
he distal axial wall he
thatdistal
was initiated
axial wallfrom
that was
the distal
initiated
marginal
from theridge
distal
on marginal
the occlusal
ridge on the occlusal
surface of the upper surface
molarofzirconia
the upper
crown.
molarFracture
zirconiafailures
crown.areFracture
observedfailures
only near
are observed only near
the top surface on the
the top
proximal
surfacemarginal
on the proximal
ridge, especially
marginal when
ridge,a thick
especially
veneering
when a thick veneering
porcelain shell is present.
porcelain
Forshell
further
is present.
details see
ForSection
further details
5.2.5, Figure
see Section
5.19 and
5.2.5,
Figure
Figure 5.19 and Figure
5.20.2–10 5.20.2–10
prepared decarburized steel. Porcelain enamels for aluminum are normally one-coat
systems that are applied by spray.
Reference
Rambaldi et al. (2007) replaced part of the potassium and sodium feldspathic sands
with soda lime–silicate glass powder in the production of whiteware bodies. The
results showed that the incorporation of glass powder up to 6%, by weight, could
produce porcelain bodies with properties, mineralogical composition and firing
behaviour similar to those of traditional porcelain.
 Rambaldi et al. (2007) replaced part of the potassium and sodium feldspathic sands
with soda lime–silicate glass powder in the production of whiteware bodies. The
results showed that the incorporation of glass powder up to 6%, by weight, could
produce porcelain bodies with properties, mineralogical composition and firing
behaviour similar to those of traditional porcelain.

Tarvornpanich et al.Tarvornpanich
(2005) produced et al.porcelain
(2005) produced
bodies containing
porcelain bodies
0%–25%, containing
by 0%–25%, by
weight, of nephelineweight,
syenite,
of nepheline
a rock thatsyenite,
consistsa largely
rock thatof consists
nepheline largely
and alkali
of nepheline and alkali
feldspar, which wasfeldspar,
replacedwhich
by soda
waslime–silicate
replaced by GC.sodaThelime–silicate
results showedGC. Thethatresults showed that
the batch containingthe6.25%
batch GC,
containing
fired at6.25%
1100°C, GC,had
fired
theatbest
1100°C,
physicalhadproperties,
the best physical properties,
giving near 0% watergiving
absorption
near 0%and water
bulk absorption
density ofand2.40 g/cm
bulk density
3. The of
performance
2.40 g/cm3of . The performance of
glass-containing porcelains
glass-containing
was comparable
porcelainstowas thatcomparable
of commercial to that
porcelains
of commercial
fired porcelains fired
at 1200°C, suggesting
at 1200°C,
that thesuggesting
use of GC thatin the
theproduction
use of GC of in porcelain
the production
bodiesofhad
porcelain bodies had
the benefits of reducing
the benefits
materialof cost
reducing
and lowering
material firing
cost and temperatures.
lowering firing In another
temperatures. In another
study (Jackson et al.,
study
2004),
(Jackson
in which
et al.,
soda 2004),
lime–silicate
in which glass
soda lime–silicate
was also usedglass as a was also used as a
replacement for nepheline
replacementsyenite,
for nepheline
it was found syenite,
that GC
it was
couldfound
act as
thatanGCextremely
could act as an extremely
strong flux, as onlystrong
aroundflux,9%asGC only
wasaround
required
9%toGC achieve
was required
performanceto achieve
similar
performance similar
to that of porcelaintomade
that of
with
porcelain
15% mineral
made flux.
with However,
15% mineral using
flux.GCHowever,
as the soleusing GC as the sole
flux generated an unacceptably
flux generatedshort an unacceptably
firing range, short
whereasfiring a mixture
range, whereas
of GC and a mixture of GC and
mineral flux allowed mineral
a greater
fluxwindow
allowedin a greater
terms ofwindow
attaining in terms
the maximum
of attainingdensity
the maximum density
and minimum water andabsorption.
minimum water absorption.

Tucci (2004) analysed

Tucci
the(2004)
effectanalysed
of replacing
the effect
up to of
20%replacing
of sodium
up to
feldspar
20% ofwith
sodium feldspar with
soda lime–silicate glass
soda lime–silicate
on the properties
glassofonporcelain.
the properties
The authors
of porcelain.
observed
Thethat
authors observed that
the optimum replacement
the optimum
level was
replacement
10% GC,levelat which
was 10%
a considerable
GC, at which
decrease
a considerable
in decrease in
firing temperaturefiring
and improved
temperature
mechanical
and improved
performance
mechanical
were performance
observed. Similar
were observed. Similar
findings were made findings
by Wannagon
were made
et al.by
(2012)
Wannagon
in the production
et al. (2012)of
inporcelain
the production
bodiesof porcelain bodies
containing glaze sludge
containing
and by
glaze
Yürüyen
sludge
and
and
Toplan
by Yürüyen
(2009) in
andthe
Toplan
production
(2009) of
in the production of
porcelain containing
porcelain
25% flycontaining
ash and 50%
25%kaolin
fly ash
in and
addition
50% tokaolin
the potassium
in addition to the potassium
feldspar and wastefeldspar
glass. and waste glass.
Porcelain is considered as the ceramic that has the longest traditions in terms of its
use as insulating material in electric engineering due to its excellent properties, such
as hardness and mechanical strength, high temperature resistance, high corrosion,
water resistance, etc. [139]. Triaxial porcelain has been the most popular material for
both low- and high-voltage insulators, and it has been used as outdoor insulators in
electric power lines for more than 150 years [140]. The term of triaxial is related to its
chemical composition which is formed by a mixture of three materials: clay, feldspar,
and silica or alumina. Each raw material gives to the porcelain distinct characteristics
[141]; the clay gives plasticity to the ceramic mixture; quartz or alumina acts as fillers
by maintaining the shape of the body during firing; and the feldspar materials serve
as flux [142]. The microstructure of fired porcelain is composed by mullite crystals
(Al6Si2O13) and undissolved quartz (SiO2) grains embedded in a continuous glassy
phase, which is formed by the feldspar and other low melting impurities in the raw
materials [142].
 Porcelain is considered as the ceramic that has the longest traditions in terms of its
use as insulating material in electric engineering due to its excellent properties, such
as hardness and mechanical strength, high temperature resistance, high corrosion,
water resistance, etc. [139]. Triaxial porcelain has been the most popular material for
both low- and high-voltage insulators, and it has been used as outdoor insulators in
electric power lines for more than 150 years [140]. The term of triaxial is related to its
chemical composition which is formed by a mixture of three materials: clay, feldspar,
and silica or alumina. Each raw material gives to the porcelain distinct characteristics
[141]; the clay gives plasticity to the ceramic mixture; quartz or alumina acts as fillers
by maintaining the shape of the body during firing; and the feldspar materials serve
as flux [142]. The microstructure of fired porcelain is composed by mullite crystals
(Al6Si2O13) and undissolved quartz (SiO2) grains embedded in a continuous glassy
phase, which is formed by the feldspar and other low melting impurities in the raw
materials [142].

Electrical porcelainElectrical
has technologically
porcelain has evolved
technologically
and severalevolved
R&D projects
and several
haveR&D projects have
been carried out tobeen
enhance
carried
its out
performance
to enhance through
its performance
different approaches,
through different
such approaches, such
as microstructural asreinforcement,
microstructural ceramic
reinforcement,
macroparticles
ceramicadditions,
macroparticles
particlesadditions,
size particles size
variation, development
variation,
and applications
developmentofand newapplications
glazes formulations,
of new glazes
surface
formulations,
coat- surface coat-
ings, etc. [143–146].
ings,
In the
etc.last
[143–146].
years, manufacturers
In the last years,
havemanufacturers
considered innovative
have considered innovative
strategies and newstrategies
technological
and new
initiatives
technological
as alternatives
initiatives
to take
as alternatives
competitivetoad- take competitive ad-
vantage against industrial
vantage competitors,
against industrialsuch competitors,
as advanced materials
such as advanced
or even nan-
materials or even nan-
otechnology concepts,
otechnology
based onconcepts,
the extraordinary
based onresults
the extraordinary
in other ceramic
resultssystems
in other ceramic systems
and porcelain for traditional
and porcelain and for
dental
traditional
applications
and dental
[147–153].
applications
Basically,
[147–153].
there areBasically, there are
two nanotechnology twoconcepts
nanotechnology
(Fig. 39.4)concepts
which have
(Fig.been
39.4)proposed
which havefor been
ceramic
proposed for ceramic
insulators: (1) reinforcement
insulators: of (1)porcelain
reinforcement
body through
of porcelain
nanoparticles
body through
addition
nanoparticles
to addition to
improve mechanical
improve
and electrical
mechanical
characteristics;
and electrical
andcharacteristics;
(2) surface nanocoatings
and (2) surface
to nanocoatings to
enhance hydrophobicity
enhanceandhydrophobicity
self-cleaning capacity
and self-cleaning
of porcelain.
capacity of porcelain.
Figure 39.4. Nanotechnology
Figure 39.4.concepts
Nanotechnology
for ceramic
concepts
insulators
for ceramic
[154,155].
insulators [154,155].
demonstrated that BN nanoparticles increase the thermal conductivity (75%) and
improve the heat corrosion and weather resistance of a fluororesin-based coating,
as well as prolonging its service life [162]. In 2016, Li et al. and Yan et al. found that
ceramic insulators coated with a novel hydroxy-terminated polydimethylsiloxane
modified nanosilica/carbon hybrid coating, exhibit better anti-icing resistance and
higher flashover performance [163,164]. Ramalla et al. developed a novel technique
to improve the environmental resistance of ceramic insulators by the application of a
nanosize powdered coating base SiO2 [165]. Similarly, Li et al. reported a nanostruc-
tured coating based on n-SiO2 that shows a super-hydrophobic performance [166].
In 2013, Dave et al. demonstrated the feasibility to deposit nanocrystalline hafnium
oxide (HfO2) films using DC magnetron sputtering to increase the hydrophobic
surface of ceramic insulators [167]. In a similar work, Portella et al. proposed a novel
nanoconcept related to the deposition of a nanometric titanium film on the HV
insulator surface by sputtering cold plasma technique, which showed a reduction
of 8.4% of the leakage current and an increment of hydrophobicity and chemical
resistance to weathering by chlorides compared with the uncoated insulator [168].
 demonstrated that BN nanoparticles increase the thermal conductivity (75%) and
improve the heat corrosion and weather resistance of a fluororesin-based coating,
as well as prolonging its service life [162]. In 2016, Li et al. and Yan et al. found that
ceramic insulators coated with a novel hydroxy-terminated polydimethylsiloxane
modified nanosilica/carbon hybrid coating, exhibit better anti-icing resistance and
higher flashover performance [163,164]. Ramalla et al. developed a novel technique
to improve the environmental resistance of ceramic insulators by the application of a
nanosize powdered coating base SiO2 [165]. Similarly, Li et al. reported a nanostruc-
tured coating based on n-SiO2 that shows a super-hydrophobic performance [166].
In 2013, Dave et al. demonstrated the feasibility to deposit nanocrystalline hafnium
oxide (HfO2) films using DC magnetron sputtering to increase the hydrophobic
surface of ceramic insulators [167]. In a similar work, Portella et al. proposed a novel
nanoconcept related to the deposition of a nanometric titanium film on the HV
insulator surface by sputtering cold plasma technique, which showed a reduction
of 8.4% of the leakage current and an increment of hydrophobicity and chemical
resistance to weathering by chlorides compared with the uncoated insulator [168].

Nanotechnology concepts
Nanotechnology
have beenconcepts
proposed have
andbeen
applied
proposed
to outdoor
and applied
ceramicto outdoor ceramic
insulators at both lab
insulators
and industrial
at both scale.
lab and
In industrial
comparisonscale.
withInother
comparison
applications,
with other applications,
R&D projects for HVR&D insulators
projectsare
for few,
HV insulators
however very
are interesting
few, however results
very interesting
regarding results regarding
the improvement of themechanical,
improvement electrical,
of mechanical,
and surface
electrical,
hydrophobic
and surface
characteristics
hydrophobic characteristics
have been achieved.have
Nanotechnology
been achieved.represents
Nanotechnology
a feasible
represents
alternative
a feasible
to develop
alternative
new to develop new
high-tech ceramic high-tech
insulators.ceramic insulators.
Porcelains and mullites can be obtained in tube and crucible form for service up
to temperatures ranging from 1200°C to 1650°C. Those for use up to the higher
temperatures are usually more sensitive to thermal shock and are usually the most
expensive. Tubes which are not impermeable to gases can have very good resistance
to thermal shock and give good service where a gas tight system is not required.
These tubes are also much cheaper than impermeable tubes. The cost of holding a
vacuum at very high temperatures can be very high. The same materials are used
as insulators, e.g. on thermocouples and electric heating elements, and as electrical
insulators for high voltage. Their constitution is similar to that of sillimanite and
mullite bricks.
Porcelains and mullites can be obtained in tube and crucible form for service up
to temperatures ranging from 1200°C to 1650°C. Those for use up to the higher
temperatures are usually more sensitive to thermal shock and are usually the most
expensive. Tubes which are not impermeable to gases can have very good resistance
to thermal shock and give good service where a gas tight system is not required.
These tubes are also much cheaper than impermeable tubes. The cost of holding a
vacuum at very high temperatures can be very high. The same materials are used
as insulators, e.g. on thermocouples and electric heating elements, and as electrical
insulators for high voltage. Their constitution is similar to that of sillimanite and
mullite bricks.