Original papers

INFLUENCE OF ZIRCONIA CeO2 LATTICE STABILIZING AGENT

ON BIOGLAZE COATING
ADRIANO KRAJEWSKI, ANTONIO RAVAGLIOLI, MAURO MAZZOCCHI, MARTINO LABANTI*,
TERESA LA TORRETTA*, GIOVANNI BEZZI*, GIANLORIS MINOCCARI*

ISTEC-CNR , Institute of Science and Technology for Ceramics - Italian National Research Council,
Via Granarolo 64, 480 18 Faenza, Italy
*ENEA, Department of Engineering of Materials and Processes - National Agency for Environment and Energy,
Via Ravengana 186, 480 18 Faenza, Italy

E-mail: krajewski@istec.cnr.it

Submitted February 17, 2003; accepted July 18, 2003

Keywords: Bioactive glass, Bioglaze®, Bioactive coating, Stabilised zirconia.

The aim of this research is to study in detail the behaviour of glassy bioactive coatings (Bioglazes®) on zirconia substrates
with different stabilising agents. In the case of tetragonal Ce-PSZ, some phenomena arose by applying a glaze coating. The
stabilising CeO2 undergoes to an -even partially reversible- autoredox process (CeO2-Ce2O3), caused by migration of oxygen
during the glazing process, (ZrO2 is known as a proton and oxygen radical conducer at high temperatures), with a macro-
scopic effect of a grey-green colouring of the Ce-PSZ substrate below the coated surface ("affected volume"). The migration
of oxygen can assume an extent for which at the glazing temperature, about 1300°C, it is possible the chemical equilibrium
shifts towards formation of Ce2O3. Grey-green is the own colour of Ce2O3. By eliminating the sealing action of the glaze
towards atmosphere, oxygen can diffuse back inside Ce-PSZ lattice, recovering the chemical and thermodynamic equilibrium
conditions with CeO2 and Ce2O3 and inducing a decolouring effect in the Ce-PSZ ceramic back to a light colour. The bioac-
tive glass utilised to produce the coatings is a calcium-silicophosphatic one, coded AP40.

INTRODUCTION towards monoclinic phase occurs. The problem rises for

the remarkable volume increase (3-5%) associated with
Zirconia (ZrO2) ceramic is a material more and this transformation that generates tangential stresses at
more considered for utilisation in biomedical field. In the grain boundaries, which bring to a rearrangement of
particular it is appreciated for its high toughness, very the tensional state of the whole bulk of the ceramic
high mechanical resistance to compression, sufficiently body. This leads to sudden cracking or delayed frac-
remarkable flexural strength and high chemical resist- tures, so compromising the integrity of the produced
ance to severe environment. ZrO2 exhibits suitable ceramic piece. To prevent, at least partially, such trans-
mechanical properties, perhaps better than those of alu- formation from high temperature phases to the mono-
mina ceramic [1-7]. clinic one, some specific oxides (of Ca2+, Mg2+, Y3+,
Moreover, it is highly biologically tolerated in con- Ce4+) are added during the production of zirconia pow-
tact with tissues and has very good resistance towards ders. These cations substitute randomly Zr4+ in its crys-
physiological and biochemical actions. tallographic lattice site and consequently are here
Good mechanical performances of zirconia, suit- defined as lattice stabilising agents (LSA).
able for biomedical applications, derive from its high Other possible problems concern the sensitivity of
temperature phases, cubic or tetragonal; instead, the stabilised zirconia ceramic to warm wet environment
monoclinic phase, stable at room temperature, does not [21], such as that of an autoclave (in case of sterilisa-
assure such performances. This is the source of the tion), and even to ageing in liquid environment, like the
problems that, together with the high specific gravity, physiological ones [11]. Possible surface modifications
let perplexed the biomedical experts for a wide use of can involve microstructural rearrangement with phase
this material. The main problem is that it is necessary to transformation, in particular with ageing [8].
sinter ZrO2 powders at high temperatures, where cubic On the other hand, zirconia ceramic material is
or tetragonal phases are stable, to obtain a zirconia unfortunately not able to exert some important biologi-
ceramic; but, during cooling, a phase transformation cal performances such as bioactivity, osteoconduction,

Ceramics − Silikáty 47 (4) 121-131 (2003) 121

 A. Krajewski, A. Ravaglioli, M. Mazzocchi, M. Labanti, T.M.G. La Torretta, G. Bezzi, L. Minoccari

osteointegrativity. Therefore, to impart (at least on the All cylinders were fired at 1000°C and sized by
surface) some of these characteristics, a coating (glaze) machining. Sintering was carried out at 1550°C for 1
with a bioactive glass (Bioglaze®) [9-13] was con- hour, and discs with a thickness of about 8 mm and diam-
ceived. This coating must have the capability to adhere eter of 25 mm were obtained by cutting the cylinders.
firmly on the surface of the zirconia ceramic substrate At the end four types of zirconia ceramic samples
and at the same time to develop the wanted biological (coded Z1, Z2, Z3, Z4) were at disposal, stabilised as
performances. The coating of zirconia ceramics is con- shown in table 1.
sidered useful to drive the surface of the ceramic from A bioactive glass, coded AP40, elsewhere charac-
inert to biologically active and osteoconductive for a terized in detail, proved useful in the role of "biogla-
close joining with bone when implanted in-vivo. The zing". Its composition is reported in table 2. It was pre-
coating in this case is also useful to prevent any possi- pared by melting in a platinum crucible inside a labora-
ble modification of the microstructure at the surface. tory kiln, at 1450°C, the proper raw materials in precise
To produce such a coating, with all these targets, amounts. After quenching, it was therefore ground in
the bioactive glass AP40 [25] was utilised. Previous powder at a granulometry ranging from 5 to 40 µm and
studies on ceramic samples made with tetragonal zirco- mixed with polymethylcellulose (as binder) to produce
nia, stabilised, with yttria (Y-PSZ), have proved the fea- an aqueous slurry.
sibility of coating of their surfaces with AP40 bioactive This slurry vas applied by brushing on the upper
glass [14-20, 25] without any loss of its biological per- base surface of the zirconia ceramic discs, produced as
formances. It is perhaps useful to remind that these bio- above described, to obtain the coating. A procedure was
logical performances are lost in a significant way when set up to obtain as much as possible homogeneity in
bioactive glasses are applied on the surfaces of alumina quantity, thickness and distribution of the slurry on the
ceramic samples [12] and this represents a point in the discs surface to be coated. Coating procedure consists in
favour of adoption of biomedical devices made with zir- firing samples in a laboratory kiln at 1280°C for 10 min-
conia ceramics. utes to allow the glass powder to melt and forming a
The target of this investigation was to ascertain if layer on the zirconia substrates and to consolidate it,
obtaining a glaze. The physico-chemical nature of the
possible differences of behaviour arise when a biologi-
obtained coatings was evaluated through by X-ray dif-
cal glass is applied with the same procedure on zirconia
fractometry (XRD), optical (OM) and scanning electron
stabilised with ceria (Ce-PSZ) rather than on zirconia
(SEM) microscopy techniques. SEM was equipped with
stabilised with yttria (Y-PSZ). Two amounts of LSA
an X-ray energy dispersion (EDS) micro-probe
addition for yttria and ceria were selected, at low con-
analyser.
tent and high content, both compatible within the range
Tests were also performed to measure the Ultimate
of reciprocal total miscibility with ZrO2 in forming a
Tensile Adhesive Strength (UTAS) on the discs coated
solid solution which has the wanted and comparable
with the bioactive glass, according to the relative BS
crystallo-physical and physico-mechanical characteris-
EN Standard 582:1984 "Thermal spraying determina-
tics. tion of tensile adhesive strength".

EXPERIMENTAL

Zirconia powders were prepared through sol-gel Table 1. Composition of the ceramics considered
technology. The base synthesis solution contains disper- sample code stabilised phase LSA amount (wt.%)
sants, colloids (e.g. polymethylcellulose), the sol (e.g. Z1 tetragonal Y 2O 3 5.2
nitrates) of zirconium ions and of the chosen LSA. Ceri- Z2 cubic Y 2O 3 13.4
um oxide was introduced in the zirconia lattice during Z3 tetragonal CeO2 12.0
its synthesis, by a co-precipitation process in aqueous Z4 tetragonal CeO2 20.0
medium, utilising a Ce4+ compound, as well as for Y3+.
So the powders in formation incorporated the proper
LSA in a due amount, depending on its concentration
into the solution of synthesis. An alkaline solution was
continuously added drop by drop until the wanted stoi-
chiometric proportions were reached; the precipitate Table 2. Chemical composition expressed in wt.% of oxides
was calcined, ground and spray-dried palletised, obtain- (except CaF2) of the bioactive glass AP40.
ing stabilised easy handling powders. Samples of cylin- SiO2 P 2O 5 CaO+CaF2 Na2O+K2O+MgO
drical shape were moulded by cold isostatic pressing
(2000 kg/cm2) with each of these powders. 44.3 11.2 36.9 7.6

122 Ceramics − Silikáty 47 (4) 121-131 (2003)

 Influence of zirconia CeO2 lattice stabilizing agent on bioglaze coating

RESULTS LSA before and after coating, except in the "affected

volume" (of course not present in the samples uncoated
General description of the coated samples as well). Anyway, the mean grain size of the Y-PSZ
samples (Z1 and Z2) resulted to be smaller (0.5-2 µm)
By looking accurately at the OM images coming than the size (2-5 µm) of the Ce-PSZ ones (Z3 and Z4).
from the different ZrO2 ceramic coated samples with the Moreover, while the microstructure of the Y-PSZ
indicated bioglaze and comparing them, it was dis- ceramic samples was very compact, some random clus-
closed that, while the glass layer on Y-PSZ substrates ters of close micro-cavities was revealed in the Ce-PSZ
resulted optimally deposited, clear and plain, the one ones.
applied on Ce-PSZ samples changed colour into a dark EDS analyses did not detect differences in compo-
moss-green, without homogeneity in thickness. A care- sition (even for trace elements) between affected and
ful investigation on cross-sections of these last samples not affected volumes of the Ce-PSZ ceramic samples.
has displayed two main more relevant aspects which Accurate XRD and EDS analyses on this affected vol-
were considered to be unfavourable. To describe them it ume did not revealed compositional variations, except
is necessary to make recourse to the image of figure l, weak traces of monazite phase (CePO4) closely to the
electronically recorded through a scanner directly on a glass "shell" and inside all the glass layer. This affected
vertical diametrical cross-section of a sample Z4, which volume was surely not perfused by glass; however, it is
explains what happened in the case of Ce-PSZ sub- reasonable to suppose that it contains Ce3+ ions.
strates.

Investigations on the substrate

Most of the glassy coating material originally
deposited on the Ce-PSZ discs accumulates near to their
periphery (along the perimeter) with a ring-like forma-
tion (in the figure defined as "Ce2O3-rich glass toroid"),
the maximum height of which was estimated to be
300~500 µm. Very thin deposition of glass was detect-
ed on the remaining area of the surface (the central zone Figure 1. Photographic image (enhanced contrast by graphic
of the discs). elaboration) taken on a section of the bioactive glass coated Ce-
Further, optical microscopy investigations on cross PSZ disk sample. Sketched characteristic structures produced by
the glass coating are reported.
sections of these discs revealed a singular grey-green
colour involving the inner body of the substrate (visible
even with the naked eye). The volume of material that
underwent such a change of colour is defined "affected
volume" in figure 1.
Measurements of the maximum extension of this
darker zone have supplied relevant values in depth
inside the samples section, but never reaching the oppo-
site side of the discs.
The colouring looks like the one of the inner part of
the glass coating ring-shaped surface: this visibly dark-
er (as above grey-green) core of the Ce-PSZ coated sub-
strate is not related to a glass penetration, as apparently
would seem at a first sight interpretation. The penetra-
tion of the glass across the interface into the ceramic
substrate was ascertained not to overcome 10 µm depth
for Ce-PSZ samples (figure 2). The layer formed by the
glass infiltration into the ceramic body was defined as Figure 2. SEM observation at the interface between AP40
"shell" as in figure 1. bioglaze and Ce-PSZ ceramic substrate (sample Z4). The dark-
er zones inside the shell, below the glass layer, are not primary
A careful SEM investigation on the ceramic
pores but the effect of permeation of glass and consequent
microstructure was therefore carried out on cross-sec- enlarging of the microstructure of ceramic substrate. True pores
tioned and polished samples, before and after deposition (e.g. internal gaps in densification) are the sparse darker spots in
of the bioglaze. Except the peripheral parts (near the the inner ceramic body. The size of the grains of the shell zone
interface with deposited glass, indicated as "shell" in is visibly increased, with the intergranular space filled by the
figures 1 and 2), the ceramic microstructure did not glassy phase that acts as cementing medium. This behaviour is
exhibit modifications among the samples with same common to both Y-PSZ and Ce-PSZ ceramics [16].

Ceramics − Silikáty 47 (4) 121-131 (2003) 123

 A. Krajewski, A. Ravaglioli, M. Mazzocchi, M. Labanti, T.M.G. La Torretta, G. Bezzi, L. Minoccari

Investigations on the coatings XRD investigations were carried out on the coating
layers (figure 3). Trace of the monoclinic phase was
The coating of all samples (both Ce-PSZ and detected both in the affected and not-affected volume of
Y-PSZ) exhibited clearly formation of small amounts of the cross-sectioned Ce-PSZ samples. However, while
Ca5(PO4)3OH (hydroxyapatite, HA) prevalently present the intensity of the detected monoclinic phase remains
on the external surface. constantly very weak, that of the tetragonal and also
As resulting from a series of optical and SEM cubic are enormously stronger as expected. This is con-
investigations on a large number of cross-sectioned firmed also by the adhesion strength of the glass layer to
samples, the penetration of the glass into the micro- the substrate. In fact, considering UTAS measurements
structure was revealed to have occurred into the zone of listed in table 3, the adhesion strength of the bioglaze
the interface. Figure 2 shows the microstructure of the is twice higher on Y-PSZ substrates [17].
layer involved in the glass infiltration in a Z4 sample.
The glass infiltration into the ceramic body has Table 3. UTAS values coming from the adhesion of AP40 coa-
formed a "shell" zone, the depth of which was detected to ting on the different substrate indicated.
be 40÷50 µm for the Y-PSZ samples, and only 8÷10 µm
sample Z1 Z2 Z3 Z4
for the Ce-PSZ samples; moreover, it was observed that
concerning the glass penetration, the smaller depth cor- UTAS (MPa) 30 ± 3 32 ± 2 16 ± 4 15 ± 4
responded to samples stabilised with the higher amount
of LSA (and vice-versa) for both Ce-PSZ and Y-PSZ.
By comparing and crossing investigations carried
The penetration of the glass in the "shell" layer, just
out on the surfaces of the bioglaze by XRD and EDS,
below the interface coating-zirconia ceramic body, cor- carried out on cross-sections of the samples, it was ascer-
responds to an intergranular infiltration which appears tained that amount and quality of the crystalline phases
similar to a porous microstructure. However, the formed inside the glaze layer (table 4) changes in rela-
microstructure of this "shell" differs from that of the tion to the kind of LSA of the zirconia ceramic substrate.
innermost parts: as showed in figure 2, it is possible to According to a previous study [20], which reveals a
observe clearly an "inflated" microstructure, with very low solubility of zirconium ions in glass systems,
enlarged grains just below the coating interface. A con- Zr4+ was not detected in the glass coatings by EDS
siderable difference was observed by SEM in the coat- microprobe. By the way, zirconium oxide is considered
ing layer on the surface of the different samples. While to have a role as a nucleating agent in glasses [24].
on the Y-PSZ samples the glass coating retains a con- Figure 3 shows XRD patterns of glass coating of Z2
sistent thickness (~200-300 µm) in a weakly cambered (top) and Z4 (bottom) samples, which exhibit a remark-
layer, the Ce-PSZ ones, apart the above mentioned able very high [h0l] and [0kl] peaks families: this indi-
peripheral ring, exhibit a formation of a very thin cates an oriented crystallisation of such planes of calci-
(<50 µm) layer, the nature of which is not constant all um-phosphosilicate phases reported in the 11-676, 35-
over the coated surface. 327 and 33-1229 JCPDS cards.

a) b)

Figure 3. XRD patterns of glass coating of Z2 (a) and Z4 (b) samples.

124 Ceramics − Silikáty 47 (4) 121-131 (2003)

 Influence of zirconia CeO2 lattice stabilizing agent on bioglaze coating

Figure 4. Large pseudohexagonal CPS micro-crystals detected

at the interface glass/substrate (sample Z4).
Figure 5. EDS pattern of the crystalline formations visible in
the SEM micrography at left (sample Z4).

Table 4. Crystalline phases detected by XRD in the glaze coat-

ings of all kinds of considered substrates, listed following an
order of decreasing quantity.
sample Z1 Z2 Z3 Z4
CPS CPS CPS CPS
glass layer HA♣ HA♣ HA♣ HA♣
CaSiO3 CaSiO3 CePO4 CePO4
interface ZrSiO4♥ - CePO4♥ CePO4♥
affected volume - - ZrO2 ZrO2
♥: Only sporadically (ZrSiO4), or traces (CePO4);
♣: HA = Hydroxyapatite, grown apparently in epitaxy basal [002]
oriented (see figure 2);
CaSiO3 = Para-wollastonite (JCPDS 31-300);
CePO4 = Monazite (JCPDS 32-199);
CPS = Calcium-phosphosilicate, including Nagels-chmidtite fami- Figure 6. Microcrystal that emerges on the surface of the glaze
ly (JCPDS 11-676, 33-1229, 35-327), mainly Ca7(SiO4)2 (sample Z1). According to EDS and XRD investigations, the
(PO4)2 at the interface coating-substrate. chemical composition fits with that of parawollastonite
(CaSiO3).

Figure 4 shows some pseudohexagonally shaped The LSA Ce4+ is instead widely diffused in the
crystalline formations, inside the glass layer, close to glaze coating of the samples Z3 and Z4 and reacted
the interface with zirconia. These micro-crystals were chemically with the components of the glass, likely with
investigated by EDS microprobe (figure 5), revealing a formation of CePO4 (monazite), as revealed by XRD
composition in agree with a calcium-phosphosilicate (although as trace).
phase, polluted (or surrounded by polluted glass) by
cerium ions, certainly coming from the dissolved frac-
tion of Ce-PSZ grains of the substrate. DISCUSSION
This agrees with the results yielded from the large
number of XRD investigations carried out, resumed in The presence of cerium trace inside the glass indi-
table 4, which indicates also the presence of CePO4 in cates that a migration of it has taken place from sub-
Z3 and Z4 samples. Crystalline formations of pseudo- strate towards the glass coating. It is not well clear how
wollastonite (CaSiO3) and calcium-phosphosilicates cerium has migrated towards glass: what is sure is that
(CSP) were observed by SEM (figures 6, 7) particular- a fraction of it has come out from zirconia lattice. This
ly into the glaze layer of Z1 samples. possibility is supported by observing the zirconia grains
No presence of the LSA Y3+ was revealed inside the at the interface substrate/glass ("shell" layer) that have
glass of Z1 samples coating, while trace was detected changed their microstructure, clearly influenced by the
inside the Z2 one. presence of the molten glass. Optical and scanning elec-

Ceramics − Silikáty 47 (4) 121-131 (2003) 125

 A. Krajewski, A. Ravaglioli, M. Mazzocchi, M. Labanti, T.M.G. La Torretta, G. Bezzi, L. Minoccari

tron microscopy investigations on the microstructure Afterwards, it was also considered the possible role
have pointed out the enlargement of the grain size, with of oxygen, reminding that ZrO2 is a good proton and
a general morphology assumed that is more compatible oxygen radical (O•) conducer at high temperatures.
with the monoclinic phase. However, the formation of On the other hand, no evident sign of deep glass
just trace of monazite indicates presence of Ce3+. As a infiltration in Ce-PSZ ceramic, after firing treatment,
general observation, it has to be pointed out that the was observed and no ions coming from glass composi-
content of LSA for Ce-PSZ is substantially twice as for tion (Si, Ca or P) were detected inside the ceramic bulk
Y-PSZ. In the case of Z4 sample, the amount of CeO2 except, as already reported, the few microns of the
(20%) present inside the zirconia lattice, to guarantee its "shell" layer below the interface.
stability in the tetragonal phase, is so huge that really it To verify that, if at the base of the observed phe-
could be considered more a mere solid solution between nomenon of the colouring of the underlying substrate
ZrO2 and CeO2 rather than a stabilised zirconia. Even at volume, there was water or fluorine, a series of planned
this high CeO2 concentration the polycrystalline zirco- tests was carried out consisting in coating Ce-PSZ flat
nia is not a composite material because no trace of free samples with different substances listed in table 6.
cerium oxide was found (by XRD). By the way, the Each test considered one ion in turn among all those
interactions of the coating glass with the CeO2 LSA present in the coating glass which were suspected to
have still to be studied, on the ability of the glass to have a possible influence on the redox reaction (includ-
extract Ce4+ ions from zirconia. What is verified is that ing phosphate group). To realise this procedure, a suit-
the presence of a glass layer induces the Ce-PSZ mate- able substance was utilised for each test to allow inter-
rial to assume an unexpected behaviour, quite different action between the specific ion and the ceramic sur-
in comparison to that observed when the same glass is face. This trial was realized by depositing the powder
deposited on Y-PSZ. As concerns the grey-green colour of such substance on the upper surface of the ceramic
assumed by the glass deposited on Ce-PSZ ceramics sample, with and without slurry. Tests were carried out
(measured also by an UV-Vis-NIR spectrometer), it was even using Hench's Bioglass® (45S5) that does not con-
attributed to formation of Ce3+, as well supported by the tain fluorine and possible reducing agents, but it has
instead a much more low melting temperature. The
detection of the cited monazite. The grey-green colour
specimens so prepared were therefore introduced in a
in the ceramic bulk agrees better with the presence of
laboratory kiln to undergo a firing similarly to the one
Ce2O3, although this last was not directly instrumentally
above described.
detected (probably because below the XRD threshold
As depicted in table 6, neither fluorine, nor phos-
limit of sensitivity). Table 5 illustrates the correspon-
phorous, nor silicon were able to affect the ceramic sub-
dence between colours and compounds of Ce3+. How-
strate, without production of any significant colouring
ever, the amount attributable to the intense colour
effect. Also water (humidity, as H2O molecules) did not
observed may derive only from a presence of a very
produce effect, even in synergy with the above cited
reduced weight percent of Ce3+ (Ce2O3). Note that
suspected ions.
Ce-PSZ ceramic is normally light-brown coloured.
Consequently, according to what expressed in table
To explain the formation of Ce3+ from the CeO2
6, it was clearly proved that no component belonging to
contained in the zirconia ceramic substrate, some redox the glass chemical composition takes part to the invoked
reactions must be invoked: being unknown the partner redox reaction involving cerium ions.
of this redox reaction, some components present in the It is instead possible to observe that the colouring
system during the adhesion interfacial reaction of enam- effect occurs in Ce-PSZ samples only when a glassy
elling, have been taken into consideration. On the base substance covers the ceramic substrate during heating,
of the electrochemical potentials [22, 23] at first the even if it does not contain a redox partner for the Ce4+ +
considered ones were the humidity (as H2O molecules, + e- → Ce3+ half-reaction, such as in the case of the 45S5
coming from burning up of organic binders), or F2 (pre- Hench's Bioglass®.
sent in the chemistry of the coating glass).

Table 5. Correspondence between colour and possible compounds of cerium.

compound CeO2 Ce2O3 CePO4 CeF3 CeFCO3
name ceria - Monazite - Bastnaesite
phase cubic trigonal monoclinic rhombohedral hexagonal hexagonal
colour brown-white grey-green red yellow white white

126 Ceramics − Silikáty 47 (4) 121-131 (2003)

 Influence of zirconia CeO2 lattice stabilizing agent on bioglaze coating

Table 6. List of substances proposed as coating to induce comparative effects on the Ce-PSZ substrate.
coating material(s)
applied (before substance(s) or ion(s) XRD new phases formed after coating colouring structural effect
coating process: expected to react on the glaze layer or on the surface/interface effect on Ce-PSZ
1290°C/15min; with the ceramic of the substrate surface
ramp: 100°C/h)
31-300 CaSiO3-2M
glass
AP40 glass + 35-327÷11-676÷33-1229 Ca7(SiO4)2(PO4)2
polymer 9 T→M♠
+ cmc♣ slurry 9-432 Ca5(PO4)3OH
water♦
32-199 (?) CePO4
35-790 CaZrO3
CaF2 fluorine 34-394 (?) CeO2 none T→M♠ (scarce)
28-775÷4-733 CaO÷Ca(OH)2
fluorine 35-790 CaZrO3
CaF2 + cmc♣ slurry polymer 34-394 (?) CeO2 none T→M♠ (scarce)
water♦ 28-775÷4-733 CaO÷Ca(OH)2
Hench's glass# glass 47-515 Na5Zr4Si3P3O24 9 T→M♠ (?)
glass
Hench's glass# +
polymer 47-515 Na5Zr4Si3P3O24 9 T→M♠ (?)
+ cmc♣ slurry
water♦
CaHPO4 • 2H2O phosphate 41-489 (?) Ca2P2O7 (γ-phase) none -
phosphate
CaHPO4 • 2H2O +
polymer 41-489 (?) Ca2P2O7 (γ-phase) none -
+ cmc♣ slurry
water♦
SiO2 (silica) silicon - none -
silicon
SiO2 + cmc♣ slurry polymer - none -
water♦
♦ From burn out of the organic binder (cmc); ♣ Organic binder in the slurry (cmc: carboxylmethylcellulose); # Glass not containing fluorine;
♠ Martensitic microstructural transformation (tetragonal → monoclinic).

The only possible reasonable explanation, deducti- assumed by the ceramic body. In argon atmosphere, the
ble from the experimental evidences, is the occurring of samples coloured more markedly. The coloured sam-
the chemical auto-redox equation: 4CeO2 ' 2Ce2O3 + ples, not coated with glass, decoloured partially by a
O2, the equilibrium constant of which is described by: successive heating at high temperature in a normal
atmosphere and cooled slowly (table 7).
To better follow what happened, Ce-PSZ samples
were investigated also through a thermo-gravimetric
KR is the thermodynamic equilibrium constant, the analysis device (TG) in flowing argon. Their change in
brackets indicate the concentration of the reported com- weight was followed in a rated heating and cooling,
pounds, Keq indicates an equivalent term of equilibrium from 1500°C to room temperature (150°C/h). The
between CeO2 and Ce2O3 depending on the partial pres- weight change (loss) occurred only during heating and
sure of oxygen ( ). attributed to O2 released from CeO2 (buoyancy drift cor-
To demonstrate the validity of this hypothesis a rection in flowing Argon and thermal expansion of the
series of heating tests were planned. Ce-PSZ ceramic device were considered in instrumental calibration). As
samples, in discs and in fragments, coated or not with the weight decreased, the contribution of the parts of
AP40 glass, were heated in kilns with different atmo- ZrO2 were expected to be constant, while the produced
spheres (air or argon, always at normal pressure, weight loss was attributed to a decrease of CeO2 and an
101325 Pa). This series of tests allowed the identifica- increase of Ce2O3.
tion of a threshold temperature of about 900°C in air Through a series of stoichiometric calculations,
and 800°C in argon, above of which the samples from the original data coming from TG analysis it was
assumed the grey-green colour: higher the temperature possible to track back to the amounts of CeO2 and
exceeding the threshold, and more marked the colour Ce2O3.

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 A. Krajewski, A. Ravaglioli, M. Mazzocchi, M. Labanti, T.M.G. La Torretta, G. Bezzi, L. Minoccari

Table 7. List of the trials carried out to check the effect of the synergy of environmental atmosphere and heating on Ce-PSZ cera-
mic substrates.
trial # condition of the Ce-PSZ ceramic temperature (°C) kiln atmosphere colouring effect on Ce-PSZ ceramic
1 AP40 coating, no colour 1300 air darkening of the "involved volume"
2 no coating, no colour 500 air no colouring
3 no coating, no colour 700 air no colouring
4 no coating, no colour 800 air no colouring
5 no coating, no colour 900 air slightly colouring
6 no coating, no colour 1300 air total darkening of the bulk
7 no coating, no colour 1300 argon total darkening of the bulk
8 no coating; 900 air decolouration along edges and corners
Ce-PSZ coloured after trial #6

tion. In fact, as above anticipated, zirconia lattice is a

sufficiently good O• radical conducer at high tempera-
ture [26], although the speed of this latter is not very
high. This migration can assume an extent for which at
the temperature of firing it becomes possible that the
chemical equilibrium shifts to right (at least on the co-
vered side).
Consequently, depending on dimension of the sam-
ple and imperviousness (given by the microstructure of
the ceramic body) of the possible paths through which
O• radicals can migrate, if the cooling is too fast the
back-migration of O• radicals (in equilibrium with
atmospheric O2) becomes forbidden for the shrinkage of
Figure 7. Needle-like shaped CPS (Nagelschmidtite family) the crystal lattice structure and most of the situation
microcrystals found on the bioglaze coating, together with HA formed at high temperature remains stopped, as
(common in both Y-PSZ and Ce-PSZ coated samples), as observed experimentally [28, 30].
reported in table 4. In the ambit of the formulated hypothesis, the pres-
ence of the glass lowers the partial pressure of O2 (PO2)
in an extent for which at the temperature of firing it
Figure 7 shows the weight trends of CeO2 and becomes possible that the chemical equilibrium above
Ce2O3 with temperature for the sample Z4 and reports written shifts to right.
also the values of Keq calculated with the equation writ- In fact, the glass interposes itself between the
ten above. On 100 parts of the total original weight, the atmosphere of the kiln and the ceramic substrate and
80 ones of ZrO2 remain constant, and the variation con- does not allow a sufficient permeation of O2, and the
cerns the remaining 20 parts of CeO2. shape and range of the "affected volume" let one think
On the other hand, it was already observed in many that such explanation is autoconsistent. The colouring in
experiments that Ce4+ can change to Ce3+ at high tem- the Ce-PSZ ceramic bulk disappears in correspondence
peratures [27]. Literature suggests that the coherency of the geometric corners and edges of the volume of the
lattice strain of the Ce-PSZ brought about by a partial ceramic sample, far off the glass coated surface, much
reduction of Ce4+ that results in a diffusion of Ce3+ along more exposed and permeable to the hot oxidative
grain boundaries to free surfaces [29]. A partial reduc- atmosphere in the kiln during cooling. The melting
tion of Ce4+ would be favoured by the difference of glass acts likely as an insulator barrier, confining the
8-fold coordinated ionic dimensions of Zr4+ (0.84 ) and reducing conditions that occur in the ceramic body.
Ce4+ (0.97 ). This reduction produces 8-fold coordina- The glass has reacted in a small extent with the
ted larger Ce3+ ions (1.14 ) that however require a ceramic material with formation of only few CePO4,
lower amount of oxygen and the lattice is allowed to detected in the thickness of the coating and at the inter-
remain tetragonal for the production of a sufficient face (figure 3). The formation of the observed HA, par-
number of oxygen site vacancies. ticularly at the surface of the deposited glass, is attrib-
The release of the produced oxygen is possible at utable to a reaction independent from redox events
high temperature for migration towards external sur- observed, considering that it forms also on the external
faces of O• radicals (the most probable form inside the surface of the glass on Y-PSZ substrates [17]. The
crystal lattice of zirconia), thanks the structure relaxa- observed physical behaviour of the glass on the surface

128 Ceramics − Silikáty 47 (4) 121-131 (2003)

 Influence of zirconia CeO2 lattice stabilizing agent on bioglaze coating

of all Ce-PSZ samples, as well the intense colouring, literature [24] as having relative low toxic hazard (as
clearly indicates that a change in the chemistry of the well as together with calcium, gold, magnesium, potas-
glass itself occurred, which could in turn induce a sium, sodium, yttrium, the zirconium itself, and others).
change in the chemical and physical interactions at the As concerns the bioactivity of the deposited glass no
interface glass-substrate. As concerns the formation of tests were performed to ascertain if it would be unal-
the singular toroidal accumulation of the glass towards tered after pollution on the Ce-PSZ samples, at the light
the periphery of the disc-shaped samples, a lot of con- of the unsuccessful result, while it resulted unmodified
troversial physical reasons could be invoked, but these for the Y-PSZ samples. On the other hand, until now
were not identified with certainty. As the phenomenon ISO standards have certified only zirconia stabilised
appears, it looks likely enough to be connected to the with yttria as biomaterial. Results coming from this
rise of the grey-green colouring of the substrate, inter- paper bring in some way other reasons as warning at
preted as a pollution of Ce3+ inside. least for zirconia stabilised with ceria.
In this way, the kinetic speed of restoring of the
thermodynamic state during cooling is not isotropic
anymore. This is the only conceivable reason that can CONCLUSION
come from experimental trials results reported in
table 6. Through the not coated surfaces (side and bot- Surface interactions and reactions which have pro-
tom) O2 permeation is possible, but its speed is not suf- duced the singular arrangement of the glaze on the Ce-
ficient to restore completely the thermodynamic condi- PSZ substrates give rise to a degradation of adhesion
tions effective at room temperature, and consequently too, as UTAS data confirm (table 3).
some Ce2O3 remains trapped in those parts of the ceram- What is sure is that cerium ions present as LSA of
ic volume that are farther from external free surfaces. zirconia have a fundamental role in the observed beha-
The geometric profile of the boundary of the "affected viour.
volume" inside the ceramic body shows this hypothesis Consequently AP40 is (and probably many other
to be reasonable. similar bioactive glasses are) useless as coating materi-
Cerium and its compounds are not generally con- al on zirconia ceramic stabilised with ceria, but remains
sidered toxic for humans. Only a hint is made in proper very useful for the same ceramic stabilised with yttria as
previously reported [20]. Consequently, bioactive glass
AP40 can be adopted to coat Y-PSZ ceramic devices,
with formation of a good and stable coating layer.
On the contrary, Ce-PSZ ones are not able to be
coated by this glass because chemically interacting with
it, yielding a glass coatings unable for biological appli-
cations. This experience reflects also on all possible
bioactive glass compositions, all subject to react in the
same way with cerium ions. Further, if the attribution to
the decreased partial pressure of oxygen is correct,
together with the insulated conditions of the ceramic
below the glass coating, the observed redox reaction of
Ce4+ ions to Ce3+ should be observed even operating a
total surface glass coating, with a complete darkening of
the coated Ce-PSZ ceramic. However, if such device
were implanted, the presence of ions underwent to a
redox reaction, even though in the ceramic below the
Figure 8. Trend of the weight % content of CeO2 (S) and Ce2O3
glass coating, could have a reactive response also with
(T) and of the equivalent constant Keq = [Ce2O3]2/[CeO2]4 as the fluids or living structures surrounding and aggres-
they can be calculated from O2 loss determined on a DTG plot. sive on the coating, and this could lead to unpredictable
The test was carried out in a flowing argon atmosphere. biological situations. Therefore, from these conclusions
The curve of Keq () can be interpreted as the superposition of a new target of research arises aimed to a verification of
two linear trends (indicated by dashed lines ---): the first (1) at a complete satisfactory biological compatibility of zir-
a slow rate of decomposition, with equation:
conia ceramics stabilised with ceria. Formation of
Keq = -44.492 + 0.166T (K),
from room temperature up to about 1300°C; the second (2) at a
hydroxyapatite in the glaze is however a good event and
fast rate of decomposition, with equation: this may lead to unexpected developments of informa-
Keq = -9279.196 + 584T (K), tion in the study of the biological interactions of mate-
from this last temperature forward. rials, particularly for applications on Y-PSZ substrates.

Ceramics − Silikáty 47 (4) 121-131 (2003) 129

 A. Krajewski, A. Ravaglioli, M. Mazzocchi, M. Labanti, T.M.G. La Torretta, G. Bezzi, L. Minoccari

Acknowledgement 10. Kirsch M., Krajewski A., Ravaglioli A., Nieswand H.

in: Proc. 3rd Meeting and Seminar on Ceramics, Cells
This paper is part of a research project the target of and Tissues, Edited by A. Ravaglioli ed A. Krajewski,
which is to study in detail the influence of different sta- p.9-18, Faenza Editrice SpA, Faenza 1997.
bilising agents in relation to the application of bioactive 11. Ferraris M., Verné E., Ravaglioli A., Krajewski A.,
glass coatings, bioglazes®, on zirconia substrates. This Paracchini L., Vogel J., Carl G., Jana C. in: Biocera-
work was realised under MURST Program "Innovative mics, Vol. 10, p.195-198, Edited by: L. Sedel and C.
Materials" (L. 95/1995) with contract: "Studio di Bios- Rey, Elsevier Science Ltd., Cambridge 1997.
malti per il Ricoprimento di Materiali Inorganici -
12. Ferraris M., Verné E., Moisescu C., Ravaglioli A., Kra-
Study of Bioglazes for Coating of Inorganic Materials"
jewski A. in: Proc. 3rd Meeting and Seminar on Cera-
(Pos. 118.2 - Rome, 05.29, 1997).
mics, Cells and Tissues, Edited by A. Ravaglioli ed A.
Krajewski, p. 31-36, Faenza Editrice SpA Faenza 1997.
13. Datta P.K., Burnell-Gray J.S., Ward L., Ravaglioli A.,
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VLIV CeO2 JAKO STABILIZÁTORU ZrO2 Cílem práce bylo podrobnì studovat chování skelných
NA POVLAKY BIOGLAZE® bioaktivních povlakù (Bioglaze®) na zirkoniových substrátech s
rùznými stabilizátory. V pøípadì tetragonálního cerem stabili-
ADRIANO KRAJEWSKI, ANTONIO RAVAGLIOLI, zovaného zirkonia (Ce-PSZ) dochází k nìkterým jevùm. CeO2
MAURO MAZZOCCHI, MARTINO LABANTI*, stabilizátor podléhá èásteènì reversibilní redoxní rovnováze
TERESA LA TORRETTA*, GIOVANNI BEZZI*, CeO2-Ce2O 3, zpùsbené migrací kyslíku bìhem pokrýváni
GIANLORIS MINOCCARI* glazurou - ZrO2 je znám jako vodiè protonù a kyslíkových
radikálù pøi vysokých teplotách. To se makroskopicky projevu-
ISTEC-CNR , Institute of Science and Technology je šedozeleným zbarvením Ce-PSZ substrátu pod glazovaným
for Ceramics - National Research Council, povrchem („ovlivnìný objem“) díky vlastnímu zbarvení Ce2O3.
Via Granarolo 64, 480 18 Faenza, Italy Z rozsah migrace kyslíku lze odhadnout jak se pøi teplotì
*ENEA, Department of Engineering of Materials glazování kolem 1300°C posouvá rovnováha smìrem k Ce2O3.
and Processes Snížením bariérního pùsobení glazury pro atmosféru mùže kys-
National Agency for Environment and Energy, lík difundovat zpìt do møížky Ce-PSZ, obnovit rovnováhu mezi
Via Ravengana 186, 480 18 Faenza, Italy CeO2-Ce2O3 a vyvolat odbarvení Ce-PSZ na pùvodní svìtlý
odstín. Bioaktivní sklo používané na povlaky je vápenato-
køemièitofosfátové s kódovým oznaèením AP40.

Ceramics − Silikáty 47 (4) 121-131 (2003) 131