CARBON 5 0 ( 2 0 1 2 ) 3 4 4 0 –3 4 4 5

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Inhibition of the catalytic oxidation of carbon/carbon

composite materials by an aluminophosphate coating
a,*
Grégory Tricot , Nathalie Nicolaus b, Pascal Diss c, Lionel Montagne a

a
UCCS, UMR CNRS 8181, USTL-ENSCL, Villeneuve d’Ascq 59652, France
b
Messier-Bugatti, Villeurbanne 69627, France
c
Snecma Propulsion Solide, Le Haillan 33187, France

A R T I C L E I N F O A B S T R A C T

Article history: The oxidation protection property of an aluminophosphate coating used to increase the
Received 18 April 2011 lifetime of C/C composite materials has been investigated. This coating has already shown
Accepted 4 March 2012 its ability to limit the thermal oxidation at high temperatures of C/C materials and we dem-
Available online 20 March 2012 onstrate in this paper its capacity to inhibit the catalytic oxidation. This catalytic oxidation,
induced at low temperature by alkali and alkaline-earth elements (Na, K, Ca), is a crucial
issue for aeronautical applications of C/C composite materials because of the presence of
these catalytic elements in de-icing solutions used in airports. In addition, new informa-
tion about the structure of the coating, prepared through the thermal treatment of a com-
mercial aluminium phosphate solution, has been derived from XRD and solid-state NMR
investigations.
 2012 Elsevier Ltd. All rights reserved.

1. Introduction er temperatures) is a crucial issue for aeronautical applica-

Numerous aeronautical and aerospace applications have ben-
efitted during the last decades from the development of car-
bon/carbon (C/C) composite materials. The excellent
properties of such materials, like low density, high tempera-
ture mechanical stability, thermal shock resistance and high
specific strength justify their application in numerous do-
mains, including reentry vehicle protection or aircraft brake
disc [1]. However, the C/C composites applications are severely
restricted by the tendency for C/C to oxidise. The oxidation
process finally leads to fibre/matrix de-cohesion resulting in
the loss of the excellent material properties. The oxidation
has a significant effect on the properties at T > 500 C but the
process starts at temperatures as low as 350 C. The oxidation
at low temperatures can be dramatically enhanced in the pres-
ence of alkali or alkaline earth elements (Na, K, Ca, Mg) that
play the role of catalysts. The catalytic oxidation (that has to
be distinguished from the thermal oxidation occurring at high-
tions, since potassium, sodium, magnesium and calcium
acetate solutions are used as de-icing solutions in airports,
where they are directly sprayed on the airport runways [2].
Considering the extremely important issues of thermal
and catalytic oxidations for aeronautical applications, much
attention has been given to the development of Oxidation
Protection Systems (OPS). Phosphorous has been used in sev-
eral OPS formulations under many forms: elemental phos-
phorous (P) [3,4], organic phosphite esters [5], oxo/chloride
phosphorous (POCl3, PCl5) [6], phosphorous pentoxide (P2O5)
[7], ortho-phosphoric acid (H3PO4) [8,9], metallic phosphates
[9–11], but also in the formulations of phosphate based
glasses [12]. The phosphorous containing OPS appear to be
very efficient solutions at moderate temperatures but lose
their protection ability at high temperatures when phospho-
rous compounds start volatilising. When used as glassy
coatings, the phosphorous OPS act as an air-tight diffusion
barrier limiting the access of oxygen to the carbon active

* Corresponding author: Fax: +33 320436814.

E-mail address: gregory.tricot@ensc-lille.fr (G. Tricot).
0008-6223/$ - see front matter  2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2012.03.007
 CARBON 5 0 ( 20 1 2 ) 3 4 4 0–34 4 5
sites. Vitreous coatings also exhibit the well-know self heal-
ing property: when cracks occur during the utilisation, expo-
sition to temperatures higher than the glass softening point
enables the crack cicatrisation by the glass viscous flow. In
the case of ceramics coatings, the oxygen access is limited
if the C/C material pores are efficiently filled by the phospho-
rous compound. Even if both ceramics and vitreous OPS are
known to significantly reduce the thermal oxidation, the vit-
reous and self-healing OPS appear to be more efficient, be-
cause the ceramic coatings generally suffer from cracks
during the utilisation and thus do not provide an air-tight bar-
rier. The other anti-oxidation mechanism reported in the lit-
erature consists in carbon active sites poisoning [4,5]. The
poisoning process involves reactivity between C sites and
phosphorous compounds through the creation of P–C and/or
P–O–C bonds, which renders the C sites inactive for oxidation.
Both mechanisms have been proposed to explain the inhibi-
tion of the catalytic oxidation of C/C materials obtained with
organic and oxychloride phosphorous in a recent investiga-
tion [4]. However, it has also been suggested that the protec-
tion against the catalytic oxidation obtained with the
phosphorous OPS [5,13,14] could originate from the ability of
phosphorous to convert the catalytic species into inactive
phosphate compounds incapable of enhancing the C/C oxida-
tion [5]. This mechanism has never been demonstrated and
the nature of such inactive species is still unknown.
We show here the inhibition of the catalytic oxidation
allowed by an aluminophosphate coating (denotes as AlP
coating in the following), obtained through the thermal treat-
ment of a commercial aluminium phosphate solution, widely
used as binder for ceramics [15–18]. The coating structure has
been investigated in details by X-ray diffraction (XRD) and 31P
and 27Al solid state magic angle spinning nuclear magnetic
resonance (MAS-NMR) performed on a very high field spec-
trometer (18.8 T). We show that the coating completely inhib-
its the catalytic effect of potassium, sodium and calcium
acetates (denoted as KAC, NaAC and CaAC, respectively) on
the C/C oxidation.
2. Experimental procedures
2.1. Materials
The C/C composite materials, provided by the Messier-Bugatti
company, have been cut in specimens of 7 g with
25 · 20 · 8 mm3 dimensions. The commercial mono alumin-
ium phosphate (MAlP) solution used to prepare the coating
has been provided by Chemische Fabrik Budenheim (FFB705,
CFB, Germany). The acidity (defined as the atomic ratio be-
tween P and Al) of the solution used in this work is equal to
3.03. The sodium element is present as impurity in the mono
aluminium phosphate solution with a concentration of 6.5 g/
L. All the materials specifications are reported in Table 1.
2.2. Coating preparation
The first step of preparation consists in a cleaning treatment
of the C/C samples with surfactant to maximise the MAlP
impregnation inside the C/C pores. Then, ca. 300 mg of the
3441
Table 1 – The mono aluminium phosphate (MAlP) solution
specifications.
AlP solution Specification
Density 1.5
P concentration (g/L) 230
Al concentration (g/L) 66
Acidity: P/Al 3.03
Na concentration (g/L) 6.5
commercial MAlP solution are homogeneously brushed on
the surface of the C/C, leading to an average loading of
20 mg/cm2. After a drying stage at 90 C, used to remove
water, the ceramic coating is formed in situ on the surface
and inside the material by a thermal treatment finalised by
a step of 3–5 h at 700 C under argon atmosphere.
A small amount of the coating (30 mg) has been extracted
after the procedure by scratching out several protected C/C
specimens. The powder, composed of AlP coating and residual
C/C material, has been analysed by XRD but is not suitable for
the NMR investigation due to the paramagnetic character of
the C/C material. Therefore, 5 mL of the commercial MAlP solu-
tion have been thermally treated in a Pt–Au5 crucible using the
procedure allowing for the coating formation. The obtained
powder has been analysed by XRD and solid state NMR.
2.3. Aluminophosphate ceramic characterisation
The XRD analyses have been performed with a Bruker D8
Advance diffractometer equipped with an energy dispersion
detector solX on the in situ (obtained by scratching out several
AlP protected C/C specimens) and ex situ (prepared in the Pt cru-
cible) samples. The acquisition was recorded between 10 and
80, with 0.02 scan step and 1 s step time. The 31P and 27Al
MAS-NMR analyses have been performed (only on the ex situ
sample) on a very high field spectrometer (18.8 T) at 324.03 and
208.57 MHz, using a HXY-3.2 mm probe operating at a spinning
frequency of 20 kHz. The 31P acquisition has been carried out
with 32 scans, 1.6 ls pulse length (corresponding to 30 pulse),
a radiofrequency field (rf) strength of 50 kHz and a recycle delay
(rd) of 600 s, sufficient for quantitative measurements. The 27Al
spectrum has been recorded with 256 scans, a 15 pulse length of
1 ls, a liquid rf strength of 40 kHz and a recycle delay of 5 s. The
31
P and 27Al chemicals shifts have been referenced to H3PO4
(85%) and Al(NO3)3 (1 M) solutions, respectively.
2.4. Catalysts deposit
The catalysts have been deposited on the C/C surface by
brushing ca. 300 mg of catalyst acetate solution (0.5 mol/L of
catalyst), corresponding to acetate solutions with 5, 4.2 and
8 wt.% of KAC, NaAC and CaAC, respectively. A drying stage
at 90 C completed the catalysts deposit step. Typically,
300 mg of catalyst solution led to a deposit of 12–15 mg of cat-
alyst acetate on the C/C samples.
2.5. Oxidation tests
The oxidation process has been investigated through C/C
weight losses occurring during isothermal treatments
3442 CARBON
performed on unprotected and AlP protected C/C samples on
which one given catalyst (K, Na or Ca) has been deposited.
The tests have been carried out in an electric furnace at
650 C (temperature representative of the C/C material appli-
cations) and the repeatability has been checked on three dif-
ferent C/C samples. The error on the normalised weight loss
(defined as Dm/m) is estimated to ±2%.
3. Results
3.1. AlP coating characterisation
The X-ray diffraction analysis performed on the AlP coating is
reported in Fig. 1. The diffraction peaks pattern clearly indi-
cates a crystalline structure and the phase identification per-
formed with the pdf database [19] highlights the presence of
aluminium tetra-metaphosphate Al(PO3)3 [A] (pdf: 13-0430)
[20]. The presence of this phase on the C/C specimens is con-
firmed by the XRD analysis performed on the in situ sample
(not shown here), indicating that the thermal evolution of
the aluminophosphate solution is not affected by the pres-
ence of carbon and leads to the formation of similar com-
pound. Many polymorphs of aluminium metaphosphate
have been identified and the polymorph [A] corresponds to
a cubic structure, where the phosphate network is consti-
tuted by cycles of 4 PO3
4 tetrahedra interconnected by octahe-
dral aluminiums [20]. This polymorph is the high temperature
form of Al(PO3)3 and melts at 1300 C.
The isotropic regions of the 31P and 27Al MAS-NMR spectra
are reported in Fig. 2a and b, respectively. The 31P MAS-NMR
spectrum (Fig. 2a) is composed by a very intense narrow peak
at 50.8 ppm, characteristic of the Al(PO3)3 [A] compound
[21,22], accompanied by low intensity signals at 19.9 and
28.4 ppm, both assigned to the sodium and aluminium pyro-
phosphate phase, NaAlP2O7 [23,24]. The simulation of the 31P
MAS-NMR spectrum (including the reported isotropic region
and the complete set of spinning sidebands) with the DMfit
software [25] allows determining the molar ratio between the
Intensity (a. u.)
11 20 30
Fig. 1 – XRD analyses of the AlP coating obtained after the thermal treatment of the industrial aluminium phosphate solution.
Full squares denote the peaks reported for Al(PO3)3 [A] compound (pdf : 13-0430).
5 0 ( 2 0 1 2 ) 3 4 4 0 –3 4 4 5
P of the Al(PO3)3 compound and the P of the NaAlP2O7 phase.
This ratio of 97.0/3.0 indicates that the AlP coating is composed
of 95.5 mol% of Al(PO3)3 [A] and 4.5% of NaAlP2O7. The 27Al MAS-
NMR spectrum (Fig. 2b) confirms the presence of the Al(PO3)3 [A]
compound through the presence of the peak at 21.4 ppm [22].
The NaAlP2O7 phase is characterised by a signal centred at
14.6 ppm, as confirmed by our 27Al MAS-NMR measurement
performed directly on this phase prepared through solid-state
route (not shown here). This signal can be observed in the
27
Al analyses of the AlP coating (Fig. 2b), confirming the pres-
ence of NaAlP2O7 in the aluminophosphate OPS.
3.2. Oxidation tests
The oxidation behaviours at 650 C under air of unprotected
and AlP protected C/C materials in the presence of KAC, NaAC
and CaAC are reported in Figs. 3–5, respectively. Fig. 3b shows
a very important oxidation process induced by the potassium
acetate with a weight loss reaching 62% after 3 h of treatment.
When coated with the AlP material, the C/C weight loss is
negligible and do not exceed 0.5%. The results obtained with
the sodium acetate (Fig. 4) are similar to those exposed in
Fig. 3. The unprotected C/C material suffers from a weight
loss of 60% whereas the AlP protected sample is only affected
by a weight loss of 0.5%. The alkaline earth catalyst appears to
be less efficient since the observed weight loss after 3 h of
treatment only reaches 30% (Fig. 5). Again, the AlP protected
sample exhibits an almost inexistent weight loss (0.4%). If
Figs. 3–5b obviously show that the oxidation rates are differ-
ent when induced by alkali or alkaline-earth elements, it is
worth mentioning that the three AlP protected samples exhi-
bit similar weight losses of 0.5% (Figs. 3–5a).
4. Discussion
In order to understand the protection ability of the AlP coating
used in our experiments, a detailed characterisation of its
structure and composition is mandatory. Many papers have
40 50 60
2-Theta /
 CARBON 5 0 ( 20 1 2 ) 3 4 4 0–34 4 5 3443

* * *

-10 -20 -30 -40 -50 -60 -5 -10 -15 -20 -25
31P Chemical shift / ppm 27Al Chemical shift / ppm

Fig. 2 – High field 31P (a) and 27Al (b) MAS-NMR spectra of the AlP coating, showing the characteristic signals of Al(PO3)3 [A] and
NaAlP2O7 (labelled as *).

Oxidation time / min Oxidation time / min

0 30 60 90 120 150 180 0 30 60 90 120 150 180
0 0
(a) (a)
10 10
Weight loss / %

20 Weight loss / % 20
30 30
(b)
40 40
50 50
60 (b)
60
70 70
Fig. 3 – Isothermal oxidation of AlP protected (a) and Fig. 5 – Isothermal oxidation of AlP protected (a) and
unprotected (b) samples polluted with KAC solution (5 wt.%) unprotected (b) samples polluted with CaAC solution
measured by weight loss versus time at 650 C under air. (8 wt.%) measured by weight loss versus time at 650 C
under air.

Oxidation time / min

0 30 60 90 120 150 180 phosphate solutions [18,22,27,28]. The XRD analyses reported
0
in these studies indicate that the coating is composed of cubic
(a)
10 aluminium metaphosphate (Al(PO3)3 [A]) in case of treatment
Weight loss / %

at temperature higher than 600 C. Lower temperatures pro-

20
cess leads to the additional presence of monoclinic alumin-
30 ium metaphosphate (Al(PO3)3 [B] [26]). The global formation
of Al(PO3)3 compound from the aluminium phosphate solu-
40
tion has been thus described by the very simplistic equation
50 3H3PO4 + Al(OH)3 ! Al(PO3)3 + 6H2O that does not take into ac-
(b) count the complex and progressive polymerisation of the alu-
60
minophosphate entities [16,22,27] and the presence of
70 impurities in the commercial solution. Our XRD analysis
(Fig. 1) and the high field 31P and 27Al MAS-NMR signals at
Fig. 4 – Isothermal oxidation of AlP protected (a) and
50.8 and 21.4 ppm, respectively (Fig. 2) fully support the
unprotected (b) samples polluted with NaAC solution
previous conclusions about the composition of the AlP coat-
(4.2 wt.%) measured by weigh loss versus time at 650 C
ing. However, the NMR experiments allow for a more detailed
under air.
characterisation of the AlP coating and afford unreported in-
sights onto its structure and composition:

(i) the 31P NMR spectrum is only composed of narrow sig-

been devoted to the characterisation of the AlP compo- nals, indicating that the AlP coating is fully crystalline
unds obtained through the thermal evolution of aluminium and does not contain any vitreous part;
3444 CARBON 5 0 ( 2 0 1 2 ) 3 4 4 0 –3 4 4 5
(ii) the presence of phosphoric acid residues (H3PO4,
H4P2O7 and HPO3) that can be related to incomplete
condensation process is ruled out by the lack of signals
in the 31P MAS-NMR analyses at 0, 13 and 22 ppm
[22] and;
(iii) the coating is not only composed by the cubic aluminium
metaphosphate but also contains significant amount
(4.5%) of sodium aluminium pyrophosphate compound.
The NaAlP2O7 phase is formed during the thermal evolu-
tion of the aluminium phosphate solution through the
reaction between the sodium (present at 6.5 wt.% as
impurity) and the aluminophosphate species, even if
the exact formation mechanism has not been deter-
mined. Owing to the very low amount of NaAlP2O7 in
the coating, the XRD analyses are not capable of detect-
ing the phase, whereas the 31P resonances at 19.9 and
28.4 ppm in Fig. 2a clearly and unambiguously highlight
its presence in the aluminophosphate OPS.
Figs. 3–5b demonstrate the critical issue of catalytic oxida-
tion for the application of C/C composite materials in aero-
nautical applications. Even at low loadings (12 mg of
catalyst acetates on C/C specimens of 7 g), low temperature
(650 C) and after short time (3 h compared to the expected
lifetime of a aircraft brake disk), it appears that all the three
catalysts produce a dramatic oxidation and weight losses.
The oxidation rates depicted in Figs. 3b and 4b are similar,
indicating that the two alkali acetates exhibit the same cata-
lytic efficiency. The global oxidation rates can be extracted
from the slopes of Figs. 3 and 4b for potassium and sodium,
respectively. We calculate the global oxidation rate per mol
of catalyst defined as (((m  m0)/m0)/t/[Cat]) where m0 is the
initial C/C weight, m is the C/C weight after the oxidation
and [Cat] is the number of catalytic elements. The values ob-
tained in our study are 3.76 · 101 s1 mol1 for K and
3.70 · 101 s1 mol1 for Na. The oxidation rate induced by
the alkaline earth element is smaller (1.73 · 101 s1 mol1)
as indicated by the lower slope of Fig. 5b. This result confirms
the lower catalytic efficiency of calcium compared to the alka-
li ions, as already observed in Ref. [2].
The protection ability of the AlP coating is unambiguously
demonstrated in Figs. 3–5a. All the AlP protected C/C speci-
mens are marginally affected by oxidation (<0.5%), indepen-
dently of the chemical nature of the catalyst. Moreover, this
low value is reached after 30 min of thermal treatment in each
case and does not increase thereafter. The observed weight
losses can thus be attributed to volatilisation of adsorbed
water or to incomplete thermal evolution of the AlP coating
precursor rather than to C/C oxidation. The results depicted
in Figs. 3–5 thus indicate that the aluminophosphate OPS com-
pletely suppresses the catalytic oxidation of the C/C materials.
From these results, the oxidation protection mechanism
can be discussed. The AlP coating is probably acting as a
physical barrier preventing any contact between the catalysts,
the carbon active sites and oxygen. However, this protection
mechanism would require an air-tight barrier distributed on
the complete surface of the C/C composites to be optimum.
As shown by the NMR results, the AlP coating is fully crystal-
line and cannot provide this type of air-tight barrier. It is more
likely to believe that the coating is only capable of limiting the
contact between the catalysts and carbon active site. The ab-
sence of catalytic oxidation would thus result from a poor
interfacial contact between catalyst species and carbon sites
due to the presence of the AlP coating in the pores and at
the surface of the C/C composite. The presence of the NaAl-
P2O7 phase in the coating and the absence of any catalytic
activity also indicate the possibility of phosphorous species
to convert the catalytic species into inactive compounds.
However, as previously mentioned, it is not clearly estab-
lished if this phase appears during the formation of the coat-
ing or if it is derived from reactivity between Al(PO3)3 and the
sodium of the solution. In order to definitively state on the
scavenging protection mechanism, the reactivity between
the AlP coating and the catalysts is currently investigated in
real conditions (presence of carbon) and will be reported in
forthcoming papers.
5. Conclusion
We report on an aluminophosphate coating known to limit the
thermal oxidation of C/C composites. Unreported insights on
the coating structure have been derived from XRD and high
field solid-state MAS-NMR investigations. We show that the
AlP coating is (i) fully crystalline, (ii) does not contain any phos-
phoric acid residues and (iii) is composed of cubic Al(PO3)3 and
small amount of NaAlP2O7. Moreover, we demonstrate that the
aluminophosphate coating is capable of inhibiting the cata-
lytic oxidation of C/C composite materials, promoted by the
Na, K and Ca elements, which is at the origin of a fast degrada-
tion of the materials even at low temperatures.
Acknowledgements
The FEDER, Region Nord Pas-de-Calais, Ministere de l’Educa-
tion Nationale de l’Enseignement Superieur et de la Recher-
che, CNRS, and USTL are acknowledged for funding of NMR
spectrometers. This paper has benefited greatly from the
thoughtful insight of the anonymous reviewers.
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