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A novel approach to carbon sequestering using hydroxyapatite to incorporate significant amounts of

CO2 with potential product applications as fertiliser.
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Journal of Materials Chemistry A DOI: 10.1039/C7TA09334A

ARTICLE

Journal of Materials Chemistry A Accepted Manuscript

Nano-Scale Hydroxyapatite Compositions for the Utilization of
CO2 Recovered Using Post-Combustion Carbon Capture
Received 00th January 20xx, Duncan A. Nowickia, Janet M. S. Skaklea,b and Iain R. Gibsona,c
Accepted 00th January 20xx
Abstract: The synthesis and analysis of a sodium-carbonate co-substituted hydroxyapatite (Ca10-xNax(PO4)6-x(CO3)x(OH)2) with
potential applications in carbon capture technologies is described. A co-substituted hydroxyapatite, using NaCl as the source
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DOI: 10.1039/x0xx00000x
of sodium, containing approximately 14 wt% carbonate was successfully prepared by an aqueous precipitation reaction
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followed by a thermal treatment under a stream of CO2 gas at 500°C. In order to reach this level of carbonation, CO2 gas
was constantly supplied to the reactant mixture during precipitation. Another hydroxyapatite prepared with sodium
carbonate, Na2CO3, in non-carbonated water but following the same methodology, incorporated a higher level
(approximately 17 wt%) of carbonate. This increase was likely a result of additional carbonate provided by the sodium
carbonate starting material. The underlying aim of this work was to examine the possibility of using hydroxyapatites to
incorporate carbon dioxide from gas recovered from post-combustion carbon capture (PC-CC) techniques. As the chemical
composition of these materials resembles bone mineral, it may be possible to use the final product in agriculture as a slow-
release fertilizer and thus make use of the products.

the Netherlands developed a process8 whereby the CO2

1. Introduction generated from the combustion of waste was used in the
mineralisation of sodium hydrogen-carbonate (NaHCO3) from a
The effect which increasing levels of carbon dioxide is having on
saturated solution of sodium carbonate (Na2CO3), producing a
the earth’s climate is of worldwide concern. An IPCC report
slurry containing 40 wt% NaHCO3. This slurry was later used to
from 2014 stated that CO2 comprises roughly 65% of total
remove acidic impurities from the waste combustion flue gas
greenhouse gas emissions1, arising predominantly from fossil
stream itself. Not only did this slurry outperform solid NaHCO3
fuel powered electricity generation2. An aggressive approach to
particles, it reduced the emission of CO2 from the plant by 2000
reduce the emission of this gas is thus required to help address
tons/year8. Another example of combining CO2 capture with
climate change. One of the most developed methods for
the formation of a product with a clear technical application is
reducing emissions of CO2 from these sources is termed flue gas
using Mg-brines combined with CO2 resulting in precipitation of
separation or post-combustion carbon capture (PC-CC), where
a magnesium-hydroxy-carbonate-hydrate (MHCH) phase,
CO2 is stripped from a flue gas stream comprised of various
which contained at least 30 wt% of CO2 and could have
components such as air, water vapour and CO2, amongst others,
applications as a cement9.
using materials such as amines or solid calcium-based
In a similar manner, CO2 gas could be utilised in the synthesis of
sorbents3-7 prior to that stream’s expulsion to the wider
a single-phase carbonated hydroxyapatite. This could act as a
environment. However, instead of simply sequestering the
route to both ‘lock’ away carbon dioxide gas into a solid material
separated CO2 in a reservoir such as an exhausted oil field,
whilst also having beneficial applications. Hydroxyapatite, HA,
recent attention has focussed instead on utilising this gas in the
(Ca10(PO4)6(OH)2) is a widely-studied and adaptable calcium
production of useful materials, with the secondary benefit of
phosphate material. The hydroxyapatite lattice can
enhancing the economics of the carbon capture process itself
accommodate a large quantity of carbonate (the carbonate
by offsetting some of the capital and operating costs. For
content of bone mineral is in the range of 4-8 wt%10) owing to
example, a waste processing and energy generation company in
its ability to substitute both hydroxyl (OH) and phosphate (PO4)
groups for carbonate (CO3) groups. This is achieved through
a. Department of Chemistry, University of Aberdeen, Meston Walk Aberdeen AB24 chemical substitution mechanisms, termed A-type and B-type
3UE. substitution respectively11. A-type substitution can be attained
b. Department of Physics, University of Aberdeen, Meston Walk Aberdeen AB24

3UE. by heating the apatite in an atmosphere of CO2 and has a

c. Institute of Medical Sciences, University of Aberdeen, Foresterhill, Aberdeen AB25
theoretical maximum substitution level. The substitution of
2ZD.
Electronic Supplementary Information (ESI) available: [details of any supplementary phosphate groups for carbonate groups can be achieved by the
information available should be included here]. See DOI: 10.1039/x0xx00000x synthesis of a phosphate-deficient apatite (Ca/P > 1.67) with

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concomitant carbonate substitution introduced through the had higher carbonate content than the sample prepared using
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water used in the aqueous synthesis and/or the NaHCO3, assuming this mass loss was entirely due to CO213.
DOI: 10.1039/C7TA09334A

calcining/sintering atmosphere12. To maintain charge balance While the use of Na2CO3 could provide sources of both sodium
this substitution also requires equimolar substitution of and carbonate ions to try to maximise the carbonate
carbonate ions for hydroxyl ions. This substitution mechanism incorporation in apatite compositions, it would be beneficial to

Journal of Materials Chemistry A Accepted Manuscript

therefore has a limit on the maximum level of carbonate have the versatility to achieve high degrees of carbonation
substitution as it relies on the limiting A-type substitution. The without the need to introduce this carbonate-containing
traditional synthesis mechanism for substituting carbonate ions reagent into the reactant mixture. This would widen the
into the hydroxyapatite lattice is by co-substitution of number of routes available for carbonate incorporation into the
carbonate with a monovalent cation, typically sodium ions13,14 apatite structure by employing carbonate-free reagents during
but also ammonium15 or potassium ions16. In these examples the synthesis and therefore focussing on the introduction of
some of the calcium ions are substituted for e.g. sodium ions, carbonate solely from gas sources,
allowing more carbonate to be incorporated into the structure, The aim of the present work, therefore, was to investigate
according to the charge-balance mechanism: whether high levels of carbonation of HA could be achieved
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(PO4)3- + Ca2+  (CO3)2- + M+ using sodium chloride (NaCl) as the source of sodium ions, with
where M can be Na+, NH4+, or K+. This gives the substitution
+ carbonate ions being introduced by addition of CO2 gas into the
mechanism Ca10-xMx(PO4)6-x(CO3)x(OH2). precipitation reaction and also during calcining. Analysis of
The wide availability and low cost of sodium chloride made it an these precipitated and heated samples allowed an evaluation
attractive choice to use as the source of these co-substituting of the most favourable conditions for the carbonation of the co-
cations in this work over another more expensive reagent. substituted apatite to be made.
Moreover, with further development it may be possible to
utilise sea water directly in the synthesis of this material
although this would present its own challenges due to the 2. Experimental
presence of other dissolved ions that may substitute into the
2.1. Sample Preparation
apatite. There is extensive research on the substitution of
Sodium-carbonate co-substituted hydroxyapatite compositions
sodium ions into the hydroxyapatite lattice in pursuit of a high-
were synthesised at room temperature according to the above
quality bone replacement material, but little specifically using
formula Ca10-xMx(PO4)6-x(CO3)x(OH2). The method was based on
NaCl in the preparation of the apatite. Sodium-carbonate co-
an established aqueous precipitation method that involved
substituted hydroxyapatite, with sodium and carbonate
adding a phosphoric acid solution dropwise to an aqueous
contents in the typical range of bone mineral, was prepared by
suspension of calcium hydroxide18 with substitution values of
soaking HA prepared from calcium carbonate (CaCO3) and
0.5≤x≤3.0 (in the above formula) using NaCl as the source of
ortho-phosphoric acid (H3PO4) in a solution of NaHCO3 at 60
sodium ions in the reactant mixture. This mechanism focuses
°C17. The researchers reported that the carbonate content of
on balancing charge on the calcium and phosphate sites of HA,
the apatites increased alongside the sodium content. Apatites
with any carbonate for hydroxyl substitution considered to
with no sodium substitution displayed a carbonate content of
occur independently. Three series of apatites were precipitated
1.3 wt%; this rose to a maximum of 6.0 wt% when the degree
using each reagent; each series was identical except for the
of sodium incorporation rose to 1.5 wt%, with the vast majority
variable of the introduction of CO2 gas into the phosphate
(94%) of this carbonate situating on the B-site 17. Stephen et al.
solution reactant. The three were as follows:
substituted sodium ions into the HA structure by way of an
1) No CO2 gas was used in the first series, named “No CO2”.
aqueous precipitation reaction. In their study, compositions of
2) CO2 gas was bubbled into the phosphate reactant solution for
single-phase sodium-carbonate co-substituted HA with
approximately 30 minutes (until the pH approached pH=4) prior
substitution values of x=0.32 and Ca/P ratios of 1.70 were
to the start of addition of this solution to the Ca(OH)2
prepared using either Na2CO3 or NaHCO3 as the source of the
suspension. This was named “CO2-I”.
sodium and carbonate co-substituting cations. Their
3) CO2 gas was bubbled into the phosphate solution throughout
preparations were designed in such a way that carbonate would
the addition of this to the Ca(OH)2 suspension. The dissolution
substitute onto the hydroxyl and phosphate sites so the overall
of the CO2 gas into the water and subsequent evolution of
(Ca+Na)/(P+C) ratio was 1.67, i.e. that of a stoichiometric HA.
carbonate (CO3) and hydrogen-carbonate (HCO3) groups did not
These precipitates were subsequently sintered at 900 °C in an
affect the temperature of the phosphate solution and by
atmosphere of CO2 and H2O. Afterward, the carbonate contents
extension the reactant mixture to any significant extent. This
of these compositions were estimated by heating the samples
was named “No-CO2-ii”.
at 1300 °C for 24 hours in air and measuring the mass loss.
A calcium + sodium suspension was prepared by dissolving NaCl
Although the extent of B-type substitution (the magnitude of
(>99.5% assay, Fisher Scientific, UK) followed by dispersing
the x-value) was designed to be the same no matter which
Ca(OH)2 (98% assay, VWR, UK) in approximately 150 ml of
sodium reagent was used, the sample precipitated using Na2CO3

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distilled water, while mixed with a magnetic stirrer. value reported. Two assumptions were made in Online
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Concentrated ammonium hydroxide solution (30 ml) was added interpretation of carbon analysis in DOI: terms of reporting
10.1039/C7TA09334A

to this suspension to ensure that the pH did not fall below an carbonate contents. Firstly, it was assumed that all of the
acceptable limit (pH=9-11) to avoid the formation of calcium- carbon detected by the equipment was present as CO2 which is
deficient impurity phases19,20 upon the introduction of the reasonable as the equipment flooded the sample with oxygen,

Journal of Materials Chemistry A Accepted Manuscript

phosphoric acid solution. The phosphate solution was prepared ensuring complete combustion. The second was that any
by diluting ortho-phosphoric acid, H3PO4, (85% assay, Fisher carbon existed in the apatite structure exclusively as carbonate
Scientific, UK) with approximately 150 ml of distilled water. ions, again quite reasonable. Mixtures of stoichiometric HA and
Depending on the series that was being synthesised, if required calcium carbonate were prepared to produce samples with
known carbon contents; testing of these confirmed that the
CO2 gas was then bubbled into this solution, as described above.
analyser was accurate and precise.
Whilst the calcium-sodium suspension was placed under
constant stirring in order to avoid the formation of brushite or
monetite20,21, the phosphate solution was added dropwise over 3. Results and Discussion
a timescale of about 2 hours. This also prevents any significant
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heat being produced through exothermic reaction. After the

3.1. As-prepared apatites
complete addition of the acid, the stirring was maintained for a
XRD analysis (Figure 1) was used to determine the phase
further two hours and then the precipitate was aged overnight.
composition of the as-prepared powders to investigate the
The precipitate was filtered under vacuum and rinsed with
effect the introduction of CO2 gas into the phosphate solution
distilled water. The resultant filter-cake was dried in an oven at
had on the phase compositions of the apatite precipitates. Each
90°C then ground to a fine powder using a mortar and pestle.
obtained pattern matched the ICDD standard for
To further increase the carbonate content of the apatites, the hydroxyapatite (PDF #26-204), confirming the synthesis of a
precipitates of the series which reached the highest level of sodium-carbonate co-substituted HA which remained the
substitution (CO2-ii) before the rise of any secondary phases by major phase throughout. Relatively broad diffraction peaks
XRD were subsequently heated in a carbon dioxide atmosphere were seen in each pattern, indicating the precipitation of an
at 500 °C. Aliquots (~0.5 g) were heated in a tube furnace apatite phase made up of very small hydroxyapatite
(Model: CFS 12/3, Carbolite Gero Ltd., UK) under a CO2 gas flow crystallites23. Some of the diffraction peaks moved with rising
rate between 0.2-0.3 dm3 per minute. Samples were heated x-values, revealing changes in the d-spacing and the dimensions
from room temperature to 500 °C at 5 °C/min, held there for of the unit cells as will be discussed below. The compositions of
one hour and then cooled back down to room temperature at the CO2-ii series remained phase-pure by XRD for substitution
5°C/min. values up to and including x=2.5, the same value that was
reached when a carbonate-containing reagent (Na2CO3) was
2.2. Sample Characterisation used as the source of sodium ions (data not shown). However,
Powder X-ray Diffraction (XRD) was carried out to determine the this limit of substitution fell to x=1.0 and x=1.5 in the No-CO2
phase composition of the powders using an X’Pert Pro and CO2-i series respectively. Above these limits, small
diffractometer (PANalytical Ltd., UK) with Cu Kα radiation quantities of calcium carbonate were seen to precipitate
(λ=1.5418 Å), collecting data over a 2θ range of 15-65 ° with a alongside the apatite phase, initially as aragonite and then as a
step size of 0.013 ° and a count time of 95 s. The X-ray generator combination of aragonite and calcite at higher substitution
operated at 45 kV and 40 mA. Crystalline phases present were levels; diffraction peaks corresponding to each of these
identified using PDF files from the ICDD database: HA (#26-204), secondary phases are highlighted in Figure 1. There is evidence
aragonite (#56-090) and calcite (#28-827). The unit cell in the literature that suggests the presence of chloride ions in
parameters of the heated apatites were determined by the reactant mixture may influence the precipitation of
performing a LeBail fit on the obtained XRD patterns using aragonite24. For these compositions in the No-CO2 and CO2-i
HighScore Plus software. These fits were based on the HA series it is likely that there is insufficient carbonate in the
structural data reported by Sudarsanan and Young 22, using the reactant mixture to support co-substitution in the apatite
space group P63/m. Only the background, lattice parameters phase, so the calcium-rich composition favours formation of
and the peak shapes were refined. calcium carbonate phases. In the CO2-ii series, excess carbonate
FT-IR spectra were obtained using a Diamond/ZnSe ATR ions would be present by the constant bubbling of CO2 gas into
attached to a Spectrum Two™ (Perkin-Elmer, UK) spectrometer. the phosphate reactant throughout the addition of this solution
These absorbance spectra were collected at a 2 cm-1 resolution to the reactant mixture. This would provide sufficient carbonate
averaging 8 scans between wavenumbers of 4000 cm-1 and 400 ions to maintain co-substitution even for high values of x.
cm-1. Normalised FTIR spectra between 1800-400 and 4000-3400
The carbonate contents of the samples were determined by cm-1 for the as-prepared powders of each series are shown in
combustion infrared analysis using a CS744 Series LECO Figure 2. Figure 2(a, c, e) displays the characteristic ν1, ν2, ν3 and
carbon/sulphur analyser (LECO Instruments UK Ltd., UK); for ν4 phosphate bands at approximately 962 cm-1, 474 cm-1, 1020-
each sample duplicate measurements were made and the mean 1090 cm-1 and 570-600 cm-1, respectively, corresponding to

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DOI: 10.1039/C7TA09334A

Journal of Materials Chemistry A Accepted Manuscript

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Figure 1: Normalised X-ray diffraction patterns of dried, as-prepared apatites precipitated using NaCl with substitution values
ranging from x=0.5 to x=3.0 and differing phosphate solution conditions (a) No-CO2, (b) CO2-i and (c) CO2-ii. Peaks corresponding
to aragonite (○) and calcite (●) are marked accordingly

to synthetic hydroxyapatite25,26, which were observed in each increasing carbonate-for-hydroxyl substitution on the A-site of
sample. the apatite structure, as has been observed by Rehman and
Each of these bands remained clearly resolved even at the Bonfield25. An OH stretch band around 3570 cm-1 was also
highest substitution values. Additionally, a shoulder on the left- observed (see Figure 2(b, d, f)) at low levels of substitution,
hand side of the ν4 phosphate band at 630-640 cm-1, particularly in apatites of the No-CO2 series, behaving in the
corresponding to an OH librational vibration, was observed at same manner as the OH libration peak, again likely a
low x-values in all three series. However it progressively consequence of carbonate substitution. ν2 and ν3 carbonate
decreased in intensity as the degree of substitution rose, almost bands situated between 870-880 cm-1 and 1300-1600 cm-1
disappearing in the CO2-ii series as the limit of substitution was respectively were also present in every spectra shown in Figure
approached. This decrease in intensity may be associated with 2(a, c, e), increasing in intensity with the x-value in each series.

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DOI: 10.1039/C7TA09334A

Journal of Materials Chemistry A Accepted Manuscript

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Figure 2: Normalised FT-IR absorbance spectra of as-prepared apatites precipitated using NaCl as the source of sodium ions with
substitution values between x=0.5 and x=2.5 and differing phosphate solution conditions (a, b) No-CO2, (c, d) CO2-i and (e, f) CO2-
ii. Only single-phase samples were presented here.

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Deduction of the relative location of substituted carbonate DOI: 10.1039/C7TA09334A
groups in as-precipitated compositions of HA is problematic as
an HPO4 vibration26,27 has been reported at about 875 cm-1. The
apatites of the CO2-ii series displayed the most intense of these

Journal of Materials Chemistry A Accepted Manuscript

carbonate bands. Figure 3, which compares the intensity of
these carbonate bands across each series at a substitution value
of x=1.0, illustrates the significant effect that bubbling CO2 gas
into the phosphate solution had on the intensity of these bands.
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Figure 4: Carbonate contents of the as-prepared apatites with

substitution values between x=0.5 and x=2.5, precipitated
under each condition. Only single-phase samples are presented
Figure 3: Normalised FT-IR spectra between 900-840 cm-1 and
here. Carbonate contents of apatites precipitated using Na2CO3
1600-1300 cm-1 displaying the (a) ν2 and (b) ν3 carbonate bands
in non-carbonated water are also presented.
of as-prepared apatites precipitated using differing phosphate
solution conditions No-CO2, CO2-i and CO2-ii at a substitution
apatites precipitated using CO2 gas, regardless of the timescale
value of x=1.0.
of supply (CO2-i and CO2-ii), showed higher carbonate contents
at every x-value when compared to their counterparts
It is clear that introducing additional carbonate ions into the
synthesised without the introduction of this gas (No-CO2).
phosphate solution led to an increase in the intensity of these
Initially the difference in the carbonate content between
bands. Whilst a modest increase in intensity was seen when CO2
apatites of the CO2-i and CO2-ii series was small. For example,
was bubbled into the phosphate solution for only thirty minutes
when x=0.5, continuously bubbling CO2 gas into the phosphate
(CO2-i), it was when CO2 was bubbled in continuously (CO2-ii)
solution resulted in a carbonate content of only 4.2 wt%,
that the intensity of these bands increased significantly. It
compared to 3.8 wt% when this gas was bubbled in only prior
should be noted that for the No-CO2 series, in which no CO2 was
to addition of the phosphate solution to the Ca(OH)2
intentionally added to the reactant mixture at any time, low
suspension. However, this disparity grew with x; when the
intensity carbonate vibrations were observed for all values of x.
substitution value was increased to x=1.5, the carbonate
These syntheses were performed in air, and samples were aged
contents were 6.7 wt% and 5.8 wt% for apatites of the CO2-ii
and dried in air, providing opportunities for some atmospheric
and CO2-i series respectively. The highest value of all was seen
CO2 to be incorporated into the reaction.
in the CO2-ii series, 10.0 wt% when x=2.5, lose to three times
the maximum carbonate content seen in the No-CO2 series,
Figure 4 presents values for the quantitative analysis of
demonstrating the importance of bubbling carbon dioxide gas
carbonate contents of the as-prepared powders. In each series
into the phosphate solution when NaCl was used. This apex
of apatites, the carbonate contents were seen to rise linearly
reached using sodium chloride did fall below the degree of
with the substitution value, x (the value obtained for the x=1.0
carbonation that was achieved using Na2CO3; a single-phase
precipitate of the CO2-ii series was considered to be an outlier
apatite with 13.5 wt% carbonate was prepared in non-
with the CO3 substitution into the x=0 sample of the same series
carbonated water using that carbonate-containing reagent as
likely occurring via a different mechanism than when potassium
the source of sodium ions. Therefore, it is clear that bubbling
was co-substituted into the structure). Failing to bubble CO2 gas
CO2 gas into the phosphate solution continuously is essential to
into the phosphate solution during precipitation (No-CO2 series)
maximise the degree of carbonation of hydroxyapatite when
led to a maximum carbonate content of 3.5 wt% when x=1.0.
NaCl was used, and to approach the level obtained for co-
This carbonate most likely originated from atmospheric carbon
substitution with addition of Na2CO3.
dioxide that had dissolved into the reactant mixture. The

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where τ is the mean crystallite size in nanometres, View ArticleλOnline

the
3.2. Heated apatites wavelength of the CuKα incident radiation, DOI: θ the Bragg angle
10.1039/C7TA09334A
Figure 5 shows XRD patterns obtained from the apatites of the and B is the relative peak width where B2 = BM2 - BS2. BM is the
CO2-ii series, after being heated at 500°C in a carbon-dioxide full-width at half maximum (FWHM) in radians of the chosen
atmosphere. All of the samples still matched the PDF standard peak (the (002) reflection near 25° in this case) and BS is the

Journal of Materials Chemistry A Accepted Manuscript

for hydroxyapatite, with no secondary phases formed as a result instrumental line broadening, measured from the 111 peak of
of the thermal treatment. a silicon standard at 2θ = 28.44°. Heating the precipitates in a
CO2 atmosphere led to slightly (but consistently) smaller apatite
crystallites relative to the precipitates (see Table 1), likely a
function of further carbonate incorporation into the structure
from the thermal treatment. It should be noted that use of the
(002) peak only represents one dimension of the crystals, which
tend to be acicular28.

Table 1: Crystallite sizes (nm) of apatites as-prepared (using CO2-ii

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method) and after being heated at 500°C in CO2

x As-prepared Heated at 500°C

0 25.4 23.4
0.5 28.3 26.7
1.0 22.3 21.0
1.5 27.2 25.5
2.0 23.3 21.7
2.5 24.2 21.1
Figure 5: XRD patterns of the apatites of the CO2-ii series after
being heated at 500°C under a stream of CO2 gas.

As can be seen from the FT-IR spectra between 2000-400 cm-1

The diffraction peaks remained quite broad as might be
in Figure 6(a), the heated apatites again displayed all of the
expected for the low temperatures used, the apatites remaining
characteristic phosphate peaks previously described for the
poorly crystalline with small crystallite sizes. The Scherrer
spectra of as-prepared samples, ostensibly unaffected by the
equation28 (Equation 1), was used to evaluate the size of the
thermal treatment. The OH libration band, seen in the spectra
crystallites after heating relative to their as-prepared
of as-prepared samples as a faint shoulder on the ν4 phosphate
counterparts, assuming any strain in the lattice had a negligible
band, further decreased in intensity after the thermal
effect on the line broadening:
treatment, likely caused by additional OH-for-CO3
0.9𝜆𝜆 substitution12.
𝑡𝑡 =
𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵

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Although the OH stretching bands appeared quite weakly in the B-site. Although not used in the determination ofViewtheArticle
location
Online
precipitates of these apatites, the heat treatment effectively of the carbonate groups in the apatite, itDOI:
is worth noting that
10.1039/C7TA09334A
caused them to disappear above a substitution value of x=0.5, the profile of the ν3 carbonate band (Figure 7(b)), also changed
evidenced by the spectra between 4000-3400 cm-1 in Figure markedly after being exposed to the thermal treatment, with a
6(b). Like the precipitates, the intensity of the ν2 and ν3 peak about 1480 cm-1 and a shoulder on the left of the peak

Journal of Materials Chemistry A Accepted Manuscript

carbonate bands of the heated compositions increased with near 1415 cm-1 appearing more prominently. The measured
rising x-value. It is likely that there is significant carbonate carbonate contents of the heated apatites are presented in
substitution on the phosphate site (B-type) upon precipitation, Figure 8. As was the case with the as-prepared powders, there
originating from the CO2 gas that was provided to the reactant was a quasi-linear relationship between the substitution value
mixture, therefore many of the changes on heating the samples and the resultant carbonate content of the apatite.
in the CO2 atmosphere will be related to carbonate substituting
on the hydroxyl site (A-type) or being incorporated but not
existing on an atomic site in the HA structure (labile).
Analysis of the relative intensities of the peaks (Figure 7) that
comprise the ν2 carbonate band observed by FTIR is a common
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method for differentiating the type of carbonate that is present

in carbonate substituted HA. Fleet 29 reported that the ν2
carbonate region provides the clearest idea of the location of
these carbonate groups as it avoids the messy, overlapping
contributions that comprise the ν3 carbonate region between
1400 cm-1 and 1600 cm-1.

Figure 8: Carbonate contents of the apatites of the CO2-ii series

after being heated at 500°C under a CO2 stream. The carbonate
contents of apatites precipitated using Na2CO3 in non-
carbonated water after being heated in the same fashion are
presented for comparison..
Figure 7: FT-IR spectra of the apatites of the CO2-ii between (a)
900-840 cm-1 and (b) 1600-1300 cm-1 displaying the ν2 and ν3
carbonate bands respectively of the as-prepared (AP) and
Each of the compositions displayed a higher carbonate content
heated (500°C in CO2 atmosphere) apatites where x=2.5.
after being exposed to the thermal treatment in the carbon
dioxide atmosphere. The maximum carbonate content
observed for the heated samples precipitated using NaCl was
Upon precipitation a broad peak centred at 874 cm-1, with peak
14.0 wt% when x=2.5, however again this fell below the
asymmetry to either side of this, was obtained with poor
carbonate content of 17.4 wt% seen for an apatite precipitated
definition of distinct vibrations that may be assigned to A-type,
using Na2CO3 with equal substitution value that had been
B-type or labile carbonate. Additionally, as has been
heated following the same regime. This is a very high level of
mentioned, the contribution from probable HPO4 groups in this
carbonate substitution in the apatite structure therefore it is
region made the separation and assignment of these peaks
likely that the combined substitution of significant amounts of
even more difficult. Heating likely brought about the
carbonate and sodium will have profound effects on the
dehydration of these groups30 and the corresponding
properties such as the solubility of the material. Although there
disappearance of the HPO4 band at 875 cm-1 27, improving the
was a disparity in the carbonate contents of the apatites
peak resolution of the ν2 vibration, with a peak at high
precipitated using these two reagents at high substitution
wavenumber (~880 cm-1) appearing more distinct from the peak
values, at low levels of substitution the carbonate contents
with maximum intensity at ~871 cm-1. However, from the
were very similar, diverging after the degree of substitution
spectra of the heated apatite in Figure 7(a), it does appear that
rose above x=1.5.
the majority of the carbonate present was still situated on the

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Figueiredo et al. reported that calcining hydroxyapatite at 600 sample where x=0 was not included as the mechanism ofOnline
View Article CO3
°C caused a significant increase in the total porosity of the substitution was likely to be different). Thereafter an
DOI: 10.1039/C7TA09334A
apatite31 and so further work should be carried out to optimise expression between these two parameters for this sodium-
the heating conditions to maximise the carbonate content of carbonate co-substituted hydroxyapatite system precipitated
the apatite, either through direct substitution or adsorption on using NaCl, with a high level of carbonate incorporation was

Journal of Materials Chemistry A Accepted Manuscript

the surface. Furthermore, precipitating the apatite using NaCl developed using linear regression.
led to the inclusion of some chloride groups in final sample,
whether that be as part of the crystal structure or on the
surface, evidenced by the poisoning of the halide trap of the
equipment used to determine the sample’s carbonate content.
The development of some procedure to mitigate the presence
of this undesirable ion whilst using NaCl is essential to allow for
the synthesis of an environmentally safe material. The
separated CO2 which is to be “locked into” the apatite structure
could also be used to prepare Na2CO3, perhaps through some
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sort of modified Solvay process, which would then be used to

precipitate the apatite avoiding the issue of the chloride ions
altogether.

De Maeyer et al. reported an expression for the estimation of

the c unit cell parameter of a sodium/carbonate co-substituted
HA system as a function of the apatite’s carbonate content32,33.
In their work, only B-type substitution was present however it Figure 4: Carbonate contents plotted against c unit cell
would be beneficial if an expression could be developed for this parameters for the heated apatites of the CO2-ii series.
system where both mechanisms were exploited in order to
maximise carbonation. Unit cell parameters obtained using This extrapolates back to give unit cell dimensions at x=0 for
HighScore Plus software are shown along with unit cell volumes hydroxyapatite which are within experimental error35,36.
and measured carbonate contents (wt%) in Table 2. Additional However, there is an inherent error that will be present simply
substitution values other than the ones already presented were because the analysis was performed using apatites with a wide
prepared for additional data points. range of carbonate contents. Additionally, the unit cell
parameters were determined using diffraction patterns with
Table 2: a and c lattice parameters, carbonate contents (wt%) quite broad reflections (see Figure 5), adding another degree of
and unit cell volumes of the heated (500°C under a stream of uncertainty to the expression. Heating the apatite at
CO2) apatites of the CO2-ii series. significantly higher temperatures would have narrowed the
diffraction peaks (increased the crystallite size) but would have
x wt% CO3 a/Å c/Å V / Å3 led to the formation of impurity phases for many of the
0 4.92 9.391(3) 6.886(3) 525.91 compositions. Using a longer dwell time at 500°C may have
0.25 3.88 9.402(2) 6.893(2) 527.68 resulted in a marginal increase in the crystallite size37 thus
0.50 4.91 9.394(2) 6.893(2) 526.78 producing narrower diffraction peaks but, again, the high levels
0.75 5.64 9.399(2) 6.893(2) 529.34 of carbonation would likely be affected, as carbonate loss from
1.00 8.82 9.390(3) 6.896(3) 526.56 apatite through heating has been demonstrated to be time-
1.50 9.40 9.397(2) 6.897(2) 527.42 dependent38.
2.00 12.43 9.393(3) 6.897(3) 526.97
2.50 14.05 9.392(3) 6.900(3) 527.09 A reliable equation relating the carbonate content to the a
lattice parameter, such as those presented by De Maeyer et
al.32,33, could not be developed for the heated apatites in this
Whilst the a parameter showed no clear trend with increasing x work. The varying degrees of phosphate-for-carbonate
or wt% CO3, the c parameter generally increased along with the substitution and independent hydroxyl-for-carbonate
substitution value (and carbonate content), although the substitution meant that samples could not be compared like-
changes in this parameter were quite small. As the effective for-like with regards to trends in the a parameter, as A and B-
ionic radii of Na+ and Ca2+ are quite close (1.12 and 1.06 Å type substitution mechanisms are known to have opposite
respectively in 7-fold coordination34) it is therefore likely that effects on the unit cell parameters of the apatite. Besides,
the increasing carbonate-for-phosphate substitution is tightly controlling the extent of A-type substitution between
influencing this parameter11,32. The unit cell volume showed no successive heat treatments can be problematic12, whether that
significant change with increasing x. The values obtained for the be caused by the formation of vacancies on the A-site, changes
c parameter were plotted against each apatites’ respective in the flowrate of CO2 gas into the furnace or perhaps the loss
measured carbonate content as displayed in Figure 9 (the

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of other species such as lattice water between 250-300 °C and bone graft implants. Further, a nanoscaleViewcarbonate-
Article Online
300-400 °C causing a change in the a parameter not directly substituted apatite such as that producedDOI:in this work may have
10.1039/C7TA09334A
caused by the substitution of carbonate39. It is a combination potential application as a fertiliser/soil treatment if the
of all of these factors which lead to incredibly scattered data solubility is sufficiently high. Not only is this method sensitive
and thus a poorly fitting trend line, which would not have towards the environment, it would also improve the economics

Journal of Materials Chemistry A Accepted Manuscript

produced a substantial relationship. of post-combustion carbon capture as a whole.

The present study utilised a gas source that contained 100% CO2
and if a process based on the results described here was to be 5. Conflicts of interest
utilised in capturing CO2 from power plant waste gas a number
of considerations would need to be studied. In particular, waste There are no conflicts to declare.
gas would contain significantly less CO2 that the pure gas used
here. Additionally, the feasibility of capturing carbonate with a
precipitation reaction using a batch process may not be feasible. 6. Acknowledgments
In aqueous precipitation reactions of calcium phosphates that
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use poorly soluble calcium hydroxide as a reactant the available The authors would like to acknowledge the University of
free calcium ions in solution at any time is small, and this will be Aberdeen for providing financial support, the advice of Dr Jo
the rate limiting step of formation of the apatite phase. The Duncan with regards to the identification of phases from XRD
quantity of carbonate ions in the reaction solution at any time and Mr Colin Taylor at the UoA School of Geosciences for
does not therefore need to be high and it is envisaged that support in obtaining the carbonate analysis
continuously flowing a waste gas containing significantly less
CO2 through the phosphoric acid reactant during synthesis,
analogous to process CO2-ii, would provide sufficient carbonate 7. References
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