CSIRO PUBLISHING Full Paper

www.publish.csiro.au/journals/ajc Aust. J. Chem. 2010, 63, 83–91

Adsorption of Ink-Jet Inks and Anionic Dyes onto Mg-Al-NO3

Layered Double Hydroxides of Variable Mg:Al Molar Ratio

Anthony R. Auxilio,A Philip C. Andrews,A Peter C. Junk,A and Leone SpicciaA,B

A School of Chemistry, Monash University, Clayton, Vic. 3800, Australia.
B Corresponding author. Email: leone.spiccia@sci.monash.edu.au

Layered double hydroxides are materials that show promise as adsorbing media for ink-jet printing. In this work, layered
double hydroxides with nitrate as interlayer anions and with variable Mg:Al molar ratios ranging from 2.2 to 8.1 have been
synthesized at constant pH by the coprecipitation method and characterized by powder X-ray diffraction, N2 adsorption–
desorption, scanning electron microscopy, and helium pycnometry techniques. The ability of these materials to adsorb
ink-jet inks (BCI-Cyan, BCI-Yellow, and BCI-Magenta) and anionic dyes (CI Acid Blue 9 (AB9), CI Acid Yellow 23
(AY23), and CI Acid Red 37 (AR37)) were investigated. BCI-Yellow was found to have high affinity for material with
an Mg:Al molar ratio between 2.2 and 4.0, whereas BCI-Cyan and BCI-Magenta showed a high affinity when the Mg:Al
molar ratio was between 4.8 and 5.5. The adsorption isotherms for AB9, AY23, and AR37 on the material with Mg:Al
molar ratios 2.2–5.5 exhibited H-type curves, indicating a very strong interaction between the adsorbate and adsorbent.
Although there was no clear systematic correlation between the Mg:Al molar ratio and the Cm (dye capacity) and Ka (dye
affinity), the optimum Mg:Al molar ratio was 4.0, and this material has the potential to be used in Ink-Receptive Layer
formulation.

Manuscript received: 26 June 2009.

Manuscript accepted: 13 August 2009.

Introduction
A variety of anionic dyes are commonly used in the formulation
of aqueous-based ink-jet inks.[1–8] Examples include Acid Blue
9 (AB9), Acid Yellow 23 (AY23), and Acid Red 37 (AR37) (see
Fig. 1). These dyes contain sulfonate and carboxylate groups and
are generally used as a salt rather than in their acidic forms.[9]
They are capable of interacting with a positively charged surface
through weak (e.g. Van der Waals) and strong (e.g. electrostatic
and H-bonding) interactions.[10] However, when printing onto
a paper surface, the ink-jet dye–substrate interaction needs to
be further improved to obtain high optical density, high resolu-
tion, low image print-through to the back side of the paper and
high resistance of the image to smearing when wet.[11,12] Con-
sequently, there is continued interest in the development of solid
phases that improve dye binding properties. The Layered Double
Hydroxides (LDHs) are one family of materials currently being
investigated for this purpose.
LDHs are clays consisting of positively charged metal
hydroxide layers with interlamellar anions for charge
neutrality.[13] The general formula is: [M2+ 3+
1−x Mx (OH)2 ]
x+
[(A )x/n ·mH2 O], where M
n− 2+ and M 3+ are divalent and
trivalent cations respectively, x is the trivalent metal ratio,
M3+ /(M2+ + M3+ ), that determines layer charge density, and
An− is an exchangeable anion.[14] One family of anions are
− −
the oxo-anions that include CO2− 2−
3 , NO3 , SO4 , OH , CrO4 ,
2−
2− 2− 3−
WO4 , S2 O3 , PO4 , and others. [15] LDHs with these anions
generally have characteristic basal spacing that can be deter-
mined directly from powder X-ray diffraction (XRD) data. For
example, LDH-carbonates can be distinguished from LDH-
nitrates as they have basal spacings of ∼7.7 and 8.7 Å,
respectively, for Al/(Mg + Al) values between ∼0.20 and 0.33
(Mg:Al = 2–4).[9] LDHs are very well known for their relatively
high adsorption capacities for anionic species. This is in part due
to their relatively high surface area, positively charged surface,
high isoelectric point, and intercalation ability.
There have been few reports dealing with how variations
in M2+ :M3+ molar ratios in LDHs with different interlayer
oxo-anions influence the ability of the material to adsorb guest
anionic species into the intra- and inter-layers of LDHs. Ulibarri
and Hermosin[16] found that the MII /MIII ratio (layer charge)
and the nature of the trivalent cation (Al3+ or Fe3+ ) had no
effect on 2,4,6-trinitrophenol adsorption by anionic exchange
on the Mg-Al-CO3 system but it did for the Mg-Al-Cl system.
Studies of the sorption of radioactive iodide from aqueous solu-
tions on Mg-Al-NO3 found that 131 I− was sorbed by anionic
exchange in the interlayer of hydrotalcite with an Al/(Mg + Al)
ratio of 0.20 and that 131 I− sorption increased more than three
times for higher ratios (lower Mg:Al values).[17] Pristine Zn-Al-
NO3 -LDHs with various Zn:Al ratios (2, 2.6, and 3) have been
intercalated with 5-aminosalicylic acid using direct coprecipita-
tion and indirect ion-exchange methods.[18] For both methods,
higher intercalate loadings were found at a lower Zn:Al ratio
(owing to higher x values) together with a more ordered crystal
structure. The sorption capability of LDH for TcO− 4 could be
greatly increased by manipulating the metal cations (M2+ – Mg,
Zn, Co, Ni, Cu, Fe, Cd, Pd, and Mn; M3+ – Al, Fe, Cr, V, Y, Yb,
−
La, Ga, and Bi), interlayer anions (CO2− 2−
3 , NO3 , and SO4 ), and
−
M :M molar ratios (1 to 10). The Ni-Al-(NO3 or CO2−
2+ 3+ [19]
3 )
with Ni:Al ratio of 3:1 was found to exhibit the highest sorp-
tion capability among all the materials tested and this correlates

© CSIRO 2010 10.1071/CH09362 0004-9425/10/010083

84 A. R. Auxilio et al.

(a) N

(a)
SO
3
SO

Transmittance [%]
3 2Na

(b)
N

SO3
(b) CO
2 400
N
N N
N Fig. 2. Fourier-transform (FT)-IR spectra of (a) Mg(OH)2 and Mg-Al-
3Na
SO3
O OH
3S
H work on the effect of Mg/Al variation on adsorption properties
(c) O N SO
3
NH2
N
N can be more easily replaced with other anions than multiply
HO
2NH4

SO
3
Fig. 1. Structures of: (a) CI Acid Blue 9; (b) CI Acid Yellow 23; and
(c) CI Acid Red 37.
with the d(003) basal spacing. An increase in the anion sorption
capacity of more than two orders of magnitude accompanied
a small increase (∼0.5 Å) in the basal spacing. The adsorption
of 2,4-dichlorophenoxyacetate on Mg-Al-NO3 LDHs with dif-
ferent Mg:Al molar ratios (3.3, 2.6, and 2.1) has been studied
paying particular attention to the effect of the orientation of the
interlayer nitrate.[20] The material with an Al3+ /(Al3+ + Mg2+ )
molar ratio of 2.1 was found to exhibit low adsorption capacity
owing to the parallel orientation of the interlayer nitrate with
respect to the hydroxide sheet (small basal spacing) and thus
allowing only external adsorption, whereas the material with
a molar ratio of 3.3 (higher charge density) exhibited higher
adsorption because nitrate adopted a perpendicular orientation
relative to the hydroxide sheet (external and interlayer adsorp-
tion). Vreysen and Maes[21] investigated the adsorption of humic
and fulvic acids onto NO− − 2−
3 , Cl , and CO3 intercalated LDHs
with different Mg:Al ratios (85/15 to 60/40) and found that the
Mg:Al ratio was one factor that influenced the adsorption of
humic substances. A study of the effect of Mg:Al ratio on borate
and silicate exchange with nitrate interlayer anions found that
materials with tilted NO− 3 exchanged borate and silicate, whereas
those with flat NO− 3 did not.
[22] Thus, the adsorption behaviour
can be tuned by varying the composition of the LDH material.
We recently reported the adsorption and intercalation of AB9
on synthesized and calcined Mg-Al LDHs with CO2− 3 as coun-
terions with a focus on the effect of Mg:Al variation on its
adsorptive properties.[14,23] Optimum adsorption for the syn-
thesized LDH was in the Mg:Al range of 3.1 to 4.4, while it
was at Mg:Al ∼5.6 for the calcined counterparts. We have also
studied the adsorption behaviour of AB9, AY23, and AR37 on
(c)
(d)
900 1400 1900 2400 2900 3400
Wavenumber (1/cm)
LDH-NO3 at Mg:Al molar ratio of: (b) 8.1; (c) 5.5; and (d) 2.2.
the commercial and functionalized pseudo-boehmite.[24] Recent
of Mg/Al layered double hydroxides with NO−
3 as counter-
ions, herein referred to as Mg-Al-LDH-NO3 , showed that NO− 3
charged anions compared with CO2− 3 .
[25–29] With this in mind,
we have extended our work on novel high-performance inor-
ganic pigments for use as ink-receptive layer formulations to
the study of the dye adsorption behaviour of Mg-Al-LDH-NO3
materials. Textural properties were obtained using powder X-
ray diffraction (PXRD), scanning electron microscopy (SEM),
Fourier-transform (FT)-IR, N2 adsorption–desorption, and He
pycnometry analyses, and used to interpret the dye adsorption
properties.
Results and Discussion
Materials Synthesis and Characterization
The synthesis of Mg-Al-LDH-NO3 materials was achieved by
a coprecipitation method, as described in the Experimental
section. The Mg to Al ratio was varied from ∼2.2 to 8.1.
The materials were subjected to detailed characterization as
discussed below.
The IR spectra of Mg-Al-LDH-NO3 with Mg:Al molar ratios
of 8.1, 5.5, and 2.2 and of pure Mg(OH)2 (Fig. 2) exhibit
absorptions at 836, 1384, and 679 cm−1 due to the out-of-plane
symmetric deformation mode, antisymmetric stretching mode,
and antisymmetric deformation mode of NO− 3 , respectively.
The broad absorption centred at 3466 cm−1 can be ascribed to
O–H stretching vibrations due to interlayer H2 O. The forma-
tion of magnesium hydroxide and a concomitant reduction in
the amount of Mg-Al-LDH-NO3 is also apparent as the Mg:Al
metal molar ratio increases. The first evidence is the band at
442 cm−1 , which is due to an Al–O vibration that is intense
when Mg:Al = 2.2 and becomes less intense as the Mg:Al
molar ratio increases. This absorption was not observed in pure
Mg(OH)2 . The second evidence is the OH stretch at 3696 cm−1
that becomes apparent at Mg:Al = 6.7 and is due to the O–H
vibration of the Mg(OH)2 mineral.[30]
Powder X-ray diffractograms of the Mg-Al-LDH-NO3 mate-
rials with different Mg:Al values are shown in Fig. 3. As
−
mentioned earlier, LDHs with CO2− 3 and NO3 as interlayer
anions exhibit an average d(003) -spacing of 7.7 and 8.7 Å respec-
tively, when x (layer charge) is ∼0.25 (Mg:Al = 3.0). It is
clear that the pure phase of Mg-Al-LDH-NO3 has a larger
Adsorption of Ink-Jet Inks and Anionic Dyes
* another phase begins to evolve (magnesium hydroxide for Mg-
*
* Mg(OH)
Intensity [a.u.]
Ratio  8.1
Ratio  7.5
Ratio  6.7
Ratio  6.0
Ratio  5.5
Ratio  4.8
Ratio  4.0
Ratio  3.1
(003)
(006)
Ratio  2.2
2 12 22 32 42 52
2θ []
Fig. 3. X-ray powder diffractograms of Mg-Al-LDH-NO3 materials with
different Mg:Al values and for pure magnesium hydroxide (top trace: most
intense reflections highlighted by an asterisk).
basal spacing than Mg-Al-LDH-CO3 (see Accessory Publica-
tion, Table S1). The reason for this is that the interaction of
nitrate (single charge) with the brucite-like sheets of the LDH
is weaker than for carbonates (double charge). This results in
less compact lamellar sheets and larger basal spacing. As will be
noted later, Mg-Al-LDH-NO3 exhibited good adsorption prop-
erties within a range (2.2–5.5) of Mg:Al molar ratios. For ratios
above Mg:Al = 5.5, this type of material exhibited poor affinity
for all dyes studied. Powder X-ray analysis also revealed that an
Mg:Al = 5.5 ratio (x = 0.15) seems to be the upper limit of the
divalent to trivalent metal ratio for producing a pure phase of
this hydrotalcite-like compound. Above this molar ratio, a new
phase can be observed as revealed by the emergence of a new set
of reflections in the diffraction pattern, notably at 2θ values of
18.6◦ , 38.0◦ , and 50.8◦ (shown in asterisks).These reflections are
due to Mg(OH)2 (brucite; JCPDS no: 44–1482) that inevitably
forms as the amount of added magnesium exceeds that required
to generate the LDH phase.The trend of the d-spacing for Mg-Al-
LDH-NO3 decreases as the Mg:Al molar ratio increases (lower
x) within a range of Mg:Al molar ratio values, starting from the
highest value of 8.9 Å for Mg:Al = 2.2 to a lowest value of 8.0 Å
for Mg:Al = 4.0. However, at Mg:Al = 4.8 and above, the d-
spacing is constant (average 8.2 Å) (see Accessory Publication,
Table S1). In comparison with Mg-Al-LDH-CO3 , the d-spacing
at very low x is ∼8.1 Å. The less compact textural properties
that partly accounted for the AB9 affinity to Mg-Al-LDH-
CO3 in our previous work,[14] cannot explain the adsorption
behaviour of Mg-Al-LDH-NO3 . Although the reasoning may
be valid for AY23, it cannot explain the very low affinity of AB9
and AR37 for the Mg-Al-LDH-NO3 material with the lowest
Mg:Al value (2.2), the material with the highest d(001) spac-
ing. Previous studies[28,30] have indicated that the higher the
layer charge (lower Mg:Al), the higher the adsorption capacity
because the nitrates can be vertically oriented and thus interca-
lation can easily occur. This cannot account for the adsorption
behaviour of all dyes used in the present study. The mecha-
nism involved in the adsorption process is more complex, as
demonstrated in recent work by Marangoni et al.,[31] which found
variations in the adsorption of different bulky anionic dyes into
zinc hydroxide nitrate. Nevertheless, the current work highlights
the fact that the presence of the hydrotalcite phase is necessary in
85
order for materials to behave as excellent adsorbents. As soon as
Al-LDH-NO3 and hydromagnesite for Mg-Al-LDH-CO3 [14] ),
2
the adsorptive properties decline. The formation of Mg(OH)2 as
the Mg:Al ratio increases can be explained to simply involve the
precipitation of Mg2+ + 2OH− = Mg(OH)2 .[14] There is no sub-
sequent formation of hydromagnesite in this case because of the
CO2 -free environment during the synthesis. Note that, although
the side products (magnesium hydroxide or hydromagnesite) of
either hydrotalcite possess a very basic character, they do not
improve the adsorption behaviour of the synthesized material
(see Dye Adsorption Studies).
The physisorption isotherms (see Accessory Publication,
Fig. S1) for all Mg-Al-LDH-NO3 materials with variable Mg:Al
molar ratios were obtained via N2 adsorption–desorption analy-
62
sis. The manifestation of hysteresis loops (H3 type in this case)
on all isotherms qualifies these isotherms to be classified as type
IV.[32] Therefore, in this respect, Mg-Al-LDH-NO3 materials are
similar to Mg-Al-LDH-CO3 [14] and its calcined products.[23]
The hysteresis loop is associated with capillary condensation
taking place in mesopores and the limiting uptake over a range
of high relative pressure (p/p0 ). Aggregations of plate-like par-
ticles that can lead to slit-shaped pores are then predicted. Note
that for all materials except those with Mg:Al = 2.2 and 3.1, no
‘lower closure point’ was observed owing to the steep region
of the desorption branch expected at ∼p/p0 = 0.42 for nitrogen
at its boiling point. This is referred to as low-pressure hystere-
sis, which extends to the lowest attainable pressures. According
to Sing et al.,[32] this phenomenon may be associated with the
swelling of a non-rigid porous structure or with an irreversible
chemical interaction of the adsorbate with the adsorbent. As
noted before, the formation of Mg(OH)2 as the Mg:Al molar ratio
increases could not be avoided. The N2 adsorption–desorption
isotherm of Mg(OH)2 (see Accessory Publication, Fig. S1) is
also type IV with an H3-type hysteresis.
The surface area, pore diameter, pore volume and den-
sity of the Mg-Al-LDH-NO3 materials with different Mg:Al
molar ratios as determined using the Brunauer-Emmett-Teller
(BET) theory, Barrett-Joyner-Halenda (BJH) method and He
pycnometry are summarized in Table 1. In general, the
surface areas, densities and pore volumes of Mg-Al-LDH-
NO3 are similar to Mg-Al-LDH-CO3 reported in a previous
study,[14] but significantly lower than the calcined Mg-Al-
LDH-CO3 .[23] With respect to pore size, the trend is: Mg-Al-
LDH-CO3 > calcined Mg-Al-LDH-CO3 > Mg-Al-LDH-NO3 .
Nevertheless, these materials are mesoporous (pore diameter =
20–500 Å). Although more Mg(OH)2 forms as the Mg:Al ratio
increases, this does not appear to be reflected in the properties
derived from N2 adsorption–desorption.
The similarity in the physisorption data for the Mg-Al-LDH-
NO3 materials studied with Mg-Al-LDH-CO3 [14] having a type
IV isotherm with an H3-type hysteresis that is also similar to the
calcined products of Mg-Al-LDH-CO3 [23] suggests that these
materials have the same particle morphology. In fact, scanning
electron micrographs (Fig. 4) of Mg-Al-LDH-NO3 with differ-
ent Mg:Al molar ratios reveal the same general morphology –
hexagonal platelets. Other general observations can be made,
such as when Mg:Al ≥ 6.0, a more rounded-shape particle can
be observed in addition to more detectable large agglomerates,
which is more apparent at Mg:Al = 8.1. The morphology for
the Mg:Al = 4.8 material is noteworthy as it looks different
compared with the rest of the materials. Although the sur-
face area (121 m2 g−1 ) of this material is relatively high and
86 A. R. Auxilio et al.

Table 1. Textural properties of Mg-Al-LDH-NO3 materials at different Mg:Al values

Mg:AlA Surface areaC Average pore Corrected pore volumeD Average densityE
[m2 g−1 ] diameterD [Å] [cm3 g−1 ] [g cm−3 ]

2.2 1.5 149 0.0058 2.00

3.1 1.4 152 0.0054 1.99
4.0 51 154 0.20 1.98
4.8 121 170 0.52 1.96
5.5 130 141 0.56 1.96
6.0 115 146 0.42 1.98
6.7 112 142 0.40 1.99
7.5 109 127 0.35 2.02
8.1 98 134 0.33 2.04
Mg(OH)2 B 14 134 0.045 2.33

A Mg:Al molar ratio determined by inductively coupled plasma–atomic emission spectroscopy analysis of the
layered double hydroxide (LDH).
B Pure magnesium hydroxide (included for comparison).
C Brunauer-Emmett-Teller method.
D Barrett-Joyner-Halenda method.
E Helium density.

it generally exhibits good affinity for the three anionic dyes,
the surface looks flattened and the individual particles appear
welded. The reasons for this are unclear at present. However,
with respect to adsorptive properties, no systematic correlation
can be drawn from this observation. This is partly because the
adsorptive behaviour of these materials is different depending
on what kind of anionic dye is used.
Dye Adsorption Studies
To study adsorption behaviour, adsorption isotherms were mea-
sured for the Mg-Al-LDH-NO3 material with a Mg:Al molar
ratio between 2.2 and 6.0, as these materials exhibited the best
adsorption of ink-jet inks (see below). These studies applied
commercially available anionic dyes of known composition and
structure (see Fig. 1).
The equilibrium results for adsorption of the three dyes
onto Mg-Al-LDH-NO3 at different divalent to trivalent metal
ratios are shown in Figs 5, 6 and Accessory Publication
Figs S3–S7. According to their shape, one can obtain some
insights into the processes and mechanisms taking place between
the liquid and solid interface. Of all the materials tested,
the adsorption isotherms (Fig. 5) of Mg-Al-LDH-NO3 with
Mg:Al = 2.2 showed a peculiar behaviour towards the three dyes
used, in the sense that only one dye exhibited an isotherm that
could be fitted with the Langmuir model (AY23, Fig. 5b), but
even in this case the fit was poor. Nevertheless, this material
exhibited an H-type curve[33] expected of high-affinity mate-
rials. The initial slope of the isotherm was almost vertical,
suggesting that AY23 has a very high adsorption affinity towards
this particular type of material. Following this sharp initial
rise, adsorption continued to increase but appeared to reach
a plateau at higher dye concentrations, corresponding to satu-
ration of available sites. However, AB9 and AR37 manifested
another class of isotherm (Fig. 5a and c, respectively) that is
best described as an S-type according to the classification of
Giles et al.[33] This type of isotherm could not be fitted with
the Langmuir equation.[34] An S-type isotherm applied to this
specific system means that there is a moderate intermolecular
attraction between the adsorbate and the adsorbent and that there
is strong competition for substrate sites, from molecules of the
solvent or of another adsorbed species.
All isotherms for all anionic dyes adsorbing to Mg-Al-LH-
NO3 with a Mg:Al molar ratio between 3.1 and 6.0 (Fig. 6,
Accessory Publication Figs S2–S5) broadly exhibited a similar
shape, i.e. they can be either classified as L- or H-type. There
appears to be a general trend as to the type of shape of the
isotherm exhibited in going from a molar ratio of 2.2 to 6.0,
viz. from S-type (moderate interaction; see Fig. 5a and c) to
an L-type (strong interaction; see Fig. S2a) and then H-type
(very strong interaction; e.g. Fig. 6a–c) and finally again an
L-type (Figs S3–S5), although the traces in Figs S3–S5 are better
described as L/H hybrid-type curves. In other words, adsorbate–
adsorbent chemisorption interactions seem to be at the optimum
for the material with Mg:Al = 4.0. For the higher AY23 concen-
trations, there is a general upward swing in the amount of AY23
adsorbed on all the materials studied. Referring to the standard
system of classification[33] of adsorption isotherms, this particu-
lar behaviour is observed over the first part of an S-type isotherm,
suggesting some adsorbate–adsorbate interactions on the adsor-
bent that may be responsible for the so called ‘co-operative’
adsorption mechanism.
The dye capacities (Cm ) and binding constants (Ka ) obtained
from fitting of the data to the Langmuir equation are listed in
Table 2 for those systems where fitting was satisfactory. The
data reveal that Mg-Al-LDH-NO3 adsorbents exhibit different
affinities for the three dyes at different Mg:Al molar ratios. The
maximum Ka value of 1.1 × 106 M−1 was observed for the mate-
rial with Mg:Al = 4.0 for AB9. For AY23, Mg-Al-LDH-NO3 had
much the same affinity for this dye provided the Mg:Al molar
ratio was between 2.2 and 4.0 (average Ka is 2.4 × 105 M−1 ).
Note, however, that for this dye, the adsorption behaviour is
poorly fitted by the Langmuir equation (e.g. see Figs 5b and 6b).
Caution is therefore required in the interpretation of the fitted
parameter. It is tempting to conclude that the optimum affinity
of this type of material for the three anionic dyes is obtained with
the material having an Mg:Al ratio of 4.0. Note that the dye affin-
ity test that will be discussed later revealed that BCI-Cyan ink
has an excellent affinity for Mg-Al-LDH-NO3 with an Mg:Al
molar ratio between 4.8 and 5.5, BCI-Yellow ink has excellent
affinity for Mg-Al-LDH-NO3 with Mg:Al molar ratios between
2.2 and 4.0, whereas BCI-Magenta (red) ink exhibits excel-
lent affinities for Mg-Al-LDH-NO3 materials with Mg:Al molar
ratios between 4.8 and 5.5. The slight disagreement between
Adsorption of Ink-Jet Inks and Anionic Dyes 87

(a) (e)

500 nm 500 nm
Ratio  2.2 Ratio  5.5

(b) (f)

500 nm 500 nm
Ratio  3.1 Ratio  6.0

(c) (g)

500 nm 500 nm
Ratio  4.0 Ratio  6.7

(d) (h)

500 nm 500 nm
Ratio  4.8 Ratio  7.5

(i)

500 nm
Ratio  8.1

Fig. 4. Scanning electron micrographs of Mg-Al-LDH-NO3 with Mg:Al molar ratios of: (a) 2.2; (b) 3.1; (c) 4.0; (d) 4.8;
(e) 5.5; (f) 6.0; (g) 6.7; (h) 7.5; and (i) 8.1.

the adsorption isotherm studies using commercially available
dyes (AB9, AY23, and AR37) and the dye affinity test using
commercially available ink-jet inks (BCI-Cyan, BCI-Yellow, and
BCI-Magenta) could be due to the effect of other additives (e.g.
solvent, surfactant, biocide, buffer, chelating agent) present in
ink-jet inks.
The effect of electrostatic interaction between the surface of
Mg-Al-LDH-NO3 and the dye is difficult to rationalize for this
particular system.Theoretically,AY23 should give the highest Ka
value, followed by AB9 and then AR37. This is because AY23
and AB9 have three anionic groups, whereas AR37 has only
two. Furthermore, comparing AY23 and AB9, one of the anionic
88 A. R. Auxilio et al.

groups in AY23 is a carboxylate group, which is more basic than
sulfonates and would be expected to have higher affinity for Mg-
Al-LDH-NO3 . None of the adsorbent material studied exhibited
this kind of trend. AB9 almost always gives the highest Ka value,
followed by AR37 and then AY23. This observation suggests that
dye affinity is not solely related to the electrostatic interaction
but to other factors such as: (1) the stereochemistry of the dye on
the surface of the adsorbent; (2) the morphology of the surface
of the adsorbent; and (3) multipoint interactions.
In regard to the maximum monolayer coverage (Cm ), the data
reveal that the Mg-Al-LDH-NO3 adsorbent gives different Cm
values depending on the Mg:Al molar ratio and the adsorbate
used. For AB9, the highest Cm value (6.3 × 10−2 mmol g−1 )
can be attained at Mg:Al = 5.5, whereas it is at Mg:Al = 3.1

(a) (a)
4.0
Experimental data
(not fitted) 7
3.5
Cs [mmol g1]  102

Cs [mmol g1]  102

6
3.0
5
2.5
4
2.0
3
1.5
Experimental data
2
Langmuir
1.0

0 2 4 6 8 0 2 4 6 8
Cp [mmol mL1]  104 Cp [mmol mL1]  104

(b) (b)

Experimental data
14 Langmuir 14
Cs [mmol g1]  102

Cs [mmol g1]  102

12
12

10
10
8
8
6 Experimental data
6 Langmuir

0 5 10 15 20 25 30 35 0 10 20 30 40
Cp [mmol mL1]  104 Cp [mmol mL1]  104

(c) (c)

Experimental data 9.0

(not fitted)
8.5
Cs [mmol g1]  102

3.5
Cs [mmol g1]  102

8.0

3.0 7.5

7.0
2.5
6.5
Experimental data
6.0 Langmuir
2.0 0

15 20 25 30 35 40 0 10 20 30
Cp [mmol mL1]  104 Cp [mmol mL1]  104

Fig. 5. Adsorption isotherm for (a) Acid Blue 9; (b) Acid Yellow 23; and
(c) Acid Red 37 binding to Mg-Al-LDH-NO3 with Mg:Al = 2.2. For (b),
full line represents fitting of the data to the Langmuir equation. Cs , the
amount of dye adsorbed to the surface; Cp is the amount of dye remaining
in the solution.
Fig. 6. Adsorption isotherm for (a) Acid Blue 9; (b) Acid Yellow 23;
and (c) Acid Red 37 binding to Mg-Al-LDH-NO3 with Mg:Al = 4.0. Full
lines represent fitting of the data to the Langmuir equation. Cs , the amount
of dye adsorbed to the surface; Cp is the amount of dye remaining in the
solution.
Adsorption of Ink-Jet Inks and Anionic Dyes 89

and 4.0 for AY23 (Cm = 15 × 10−2 mmol g−1 ) and AR37
(Cm = 8.3 × 10−2 mmol g−1 ) respectively. For all the materials
studied, the general trend for the Cm value is that for all the mate-
rials studied, AY23 gave the highest value, followed by AR37 and
then AB9.
Previously,[14] it was concluded that the adsorptive capacity
(using AB9) of Mg-Al-LDH-CO3 material is a direct conse-
quence of surface area. Thus, the Mg-Al-LDH-CO3 material
with Mg:Al = 3.1 had the highest surface area (123 m2 g−1 ) and
the highest Cm value (7.6 × 10−2 mmol g−1 ). This also appears
to hold true for the Mg-Al-LDH-NO3 material provided the same
dye (AB9) is used (see Adsorption Isotherm section). In fact,
for AB9, optimum adsorption (Cm = 6.3 × 10−2 mmol g−1 ) was
observed at Mg:Al = 5.5, where the surface area (130 m2 g−1 )
is at its maximum. With respect to pore size, no correlation with
adsorptive capacity can be made with this property. As the pore
volume changes in accordance with the surface area, the same
conclusion derived from surface area with respect to the adsorp-
tive capacity can be expected. Furthermore, the average density
does not influence the adsorptive behaviour of Mg-Al-LDH-
NO3 materials as it does not change significantly as the Mg:Al
molar ratio changes. The average density (2 g cm−3 ), however,
for Mg-Al-LDH-NO3 materials is the same as for the Mg-Al-
LDH-CO3 materials reported previously.[14] Therefore, it can
also be concluded that changing the interlayer anions from CO2−
to NO− 3 does not affect the density of the material.
It should be emphasized here that above and below a molar
ratio of 5.5 for Mg-Al-LDH-NO3 , the surface area decreases
as does the adsorptive capacity for AB9. This applies to AY23
and AR37 adsorbates, which exhibited optimum adsorption
(Cm = 15.3 × 10−2 mmol g−1 ) forAY23 at Mg:Al = 3.1 (surface
area (SA) = 1.4 m2 g−1 ) and at Mg:Al = 4.0 (SA = 51 m2 g−1 )
for AR37 (Cm = 8.3 × 10−2 mmol g−1 ). Two explanations can
be proposed here: (1) different kinds of interaction can take
place between the adsorbate and the adsorbent owing to the
different number and type of anionic groups present in the
dye; and (2) even at the relatively low concentrations (5 mM)
for AY23 (3− charge) and AR37 (2− charge) used in this
study, these dyes have the potential to replace the nitrates (1−
charge) in the interlamellar region (intercalate) mainly because
of their higher charge. However, this requires further study.
It is possible that more dye is adsorbed by materials with
higher layer charge density (lower Mg:Al).[35] Note that the
work of Ulibarri and Hermosin and their coworkers[16] seems
in contradiction with the present study as discussed in our pre-
vious publication.[14] Changing the Mg:Al molar ratio clearly
affects the adsorptive capacity of Mg-Al-CO3 material. But,
the fact that Ulibarri and Hermosin reported that the adsorp-
tion behaviour of 2,4,6-trinitrophenol on the Mg-Al-Cl system
was affected by the variation of the Mg:Al molar ratio seems
to suggest the likelihood of intercalation of AY23 and AR37
in our study, as mentioned above. However, the work of Fetter
et al.[17] is in agreement with findings presented herein. This
3 shows that adsorption behavioural studies using hydrotalcite-
like materials are complex and can involve many factors such
as: (1) the procedure of sorption studies; (2) the mechanism
of adsorption (surface or interlamellar); and (3) the type of
sorbate.

Table 2. Langmuir model parameters for Acid Blue 9 (AB9), Acid Yellow 23 (AY23), and Acid Red 37 (AR37) binding to Mg-Al-LDH-NO3 system
at ratios 2.2, 3.1, 4.0, 4.8, 5.5, and 6.0
Bold entries represent the highest measured Cm and Ka values

Mg:Al molar ratio Cm [mmol g−1 ] Ka [M−1 ]

AB9 AY23 AR37 AB9 AY23 AY37

2.2 – 12.0 (±0.4) × 10−2 – – 2.53 (±0.72) × 105 –

3.1 – 15.3 (±1.2) × 10−2 – – 2.76 (±0.84) × 105 –
4.0 5.53 (±0.33) × 10−2 11.9 (±0.65) × 10−2 8.29 (±0.20) × 10−2 1.10 (±0.35) × 106 2.02 (±0.75) × 105 1.44 (±0.45) × 105
4.8 5.59 (±0.32) × 10−2 – 8.22 (±0.17) × 10−2 2.68 (±0.80) × 105 – 5.3 (±1.4) × 104
5.5 6.30 (±0.29) × 10−2 – 10.2 (±0.37) × 10−2 1.75 (±0.37) × 105 – 6.5 (±2.4) × 104
6.0 4.40 (±0.32) × 10−2 – 6.40 (±0.20) × 10−2 5.4 (±2.0) × 104 – 10.0 (±3.4) × 104

100
90
80
Dye adsorbed [%]

70
60
50
40
30 BCI-Magenta
20 BCI-Yellow
10 BCI-Cyan
0
2.2 3.1 4.0 4.8 5.5 6.0 6.7 7.5 8.1
Mg:Al molar ratio

Fig. 7. Percentage of commercial ink-jet inks (BCI-Cyan, BCI-Yellow, and BCI-Magenta) adsorbed onto the surface of Mg-Al-LDH-
NO3 at different Mg:Al molar ratios. Note: adsorbent mass = 0.5 g, T = ambient, pH of 10% ink solutions (20% v/v glycerol/water
solvent) are as follows: BCI-Cyan = 8.1, BCI-Yellow = 4.7, and BCI-Magenta = 5.4.
90
A qualitative dye affinity test was also conducted for the com-
mercial ink-jet inks to initially investigate the viability of these
materials to be used in ink-receptive layer (IRL) formulations.
The percentages of dye adsorbed for each Mg-Al-LDH-NO3
sample with different Mg:Al ratios are shown in Fig. 7. At
the outset, the materials tested have shown some affinity for
the dye in solution of varying degree, spanning from 19% for
BCI-Magenta with Mg-Al-LDH-NO3 of Mg:Al = 3.1 to 96%
for BCI-Yellow with Mg-Al-LDH-NO3 of Mg:Al = 2.2. BCI-
Yellow exhibited a different adsorption behaviour with respect
to Mg:Al molar ratios of Mg-Al-LDH-NO3 compared with
BCI-Cyan and BCI-Magenta.
The highest affinity for BCI-Yellow was found for Mg-Al-
LDH-NO3 materials with an Mg:Al molar ratio between 2.2
and 4.0, whereas for BCI-Cyan and BCI-Magenta, a high affin-
ity could be achieved with an Mg:Al molar ratio between 4.8
and 5.5. Within the Mg:Al molar ratios studied, these materials
were found to adsorb slightly more yellow dye than magenta
and cyan. This may be due to the yellow dye having more acidic
(anionic) groups available to interact with the cationic surface.
Mg-Al LDHs are well known to have a very high isoelectric point
(between 11 and 12).[36–38] Therefore, the surface is positively
charged at the pH of ink samples. Note that the pH of solu-
tions of BCI-Yellow, BCI-Magenta, and BCI-Cyan are 4.7, 5.4,
and 8.1, respectively. Currently, studies are being conducted by
the authors aimed at understanding the fundamental adsorption
mechanisms by taking into account the dye structures.
Conclusion
As part of ongoing efforts aimed at developing inorganic pig-
ments for application as media for ink-jet printing, we have
investigated the dye-adsorption properties of a series of Mg-Al-
LDH-NO3 materials with different Mg:Al molar ratios. Equi-
librium adsorption experiments, using three anionic dyes, AB9,
AY23, and AR37, indicated a very strong interaction between the
adsorbate and adsorbent for several Mg:Al ratios. The highest
binding affinities (Ka ), were observed for AB9 and AY23 and for
Mg:Al = 4.0. We note that the Langmuir equation fitted many of
the adsorption isotherms poorly, indicating that multiple adsorp-
tion mechanisms may be in operation for these materials. This
is in contrast with the behaviour of the previously reported Mg-
Al-LDH-CO3 system. In general, surface adsorption processes
showed no systematic correlation with the textural properties
of the materials. However, it can be generalized that large pore
sizes and a pure LDH phase are necessary prerequisites for this
material to behave as an excellent adsorbent for the dyes used in
this study.
Comparison of the adsorptive behaviour between Mg-Al-
LDH-NO3 with different Mg:Al molar ratios and ink-jet inks
(BCI-Cyan, BCI-Yellow, and BCI-Magenta) as adsorbate indi-
cated the ability of these dyes to adsorb varies with the material
composition. BCI-Yellow was found to have high affinity for
Mg-Al-LDH-NO3 with an Mg:Al molar ratio between 2.0 and
4.0, while BCI-Cyan and BCI-Magenta showed a high affinity
when the Mg:Al molar ratio was between 4.8 and 5.5. Physi-
cal mixing of appropriate proportions of these materials could,
therefore, be used to produce a composite material with excellent
affinity for all commercial ink-jet inks.
Experimental
Preparation of Adsorbent Material
Mg-Al LDHs with nitrates as interlayer ions (Mg-Al-LDH-
NO3 ) with varying Mg2+ :Al3+ ratios (2.2–8.1) were prepared
A. R. Auxilio et al.
at pH 9.50 (±0.05) by the modification of previously described
methods.[14,26] A typical synthetic procedure leading to a sam-
ple with Mg:Al = 2.2 (actual Mg:Al molar ratio added is 2.0)
involved the following.
Solution A was prepared by dissolving Mg(NO3 )2 ·6H2 O
(61.54 g, Sigma–Aldrich) andAl(NO3 )3 ·9H2 O (45.02 g, Sigma–
Aldrich) in water (150 mL). Solution B was prepared by dis-
solving NaOH (23.27 g, Merck) in water (150 mL). Solutions
A and B were added dropwise to a four-necked round-bottom
flask containing freshly boiled water (120 mL) under a nitrogen
atmosphere. The addition of solutions A and B was performed
with constant stirring (using a magnetic stirrer) and at ambi-
ent temperature, and at such a rate that the pH of the reaction
mixture was maintained at 9.5 (±0.05) using a Metrohm 736 GP
Titrino autotitrator. The resulting slurry was aged at 100◦ C using
an oil bath for 16 h under a nitrogen atmosphere. The precipi-
tate was filtered (no. 3 sintered filter funnel), washed twice with
deionized and decarbonated water and dried at 100◦ C for 24 h.
All products were then ground with an agate mortar and pestle
before characterization.
Preparation of Ink-Jet Inks and Anionic Dye Solutions
Commercial inks (BCI-Cyan, BCI-Yellow, and BCI-Magenta)
were diluted using 20% (v/v) glycerol/deionized water, giving a
10% (v/v) ink solution before the dye affinity test. Glycerol is
one of the common solvents used in the formulation of ink-jet
inks.[9] These inks were sold as refillers for Canon ink-jet printer
cartridges and are used in their mid-range ink-jet printers.
Commercially available dyes (Fig. 1), namely CI AB9 (AB9,
Saujanya Dyechem), CI Y23 (AY23, Sigma–Aldrich), and CI
AR37 (AR37, Sigma–Aldrich), were used to prepare dye solu-
tions consisting of 1 mM AB9, 5 mM AY23, and 5 mM AR37
using pure water (Milli-Q) taking into account the dye content
from the as-received dyes. These dye concentrations were based
on commercial ink-jet ink concentrations mentioned above (note
that AB9 has a higher ε value). Table 3 lists the wavelength
of maximum absorbance (λmax ) and molar absorptivity (ε) for
each dye.
Characterization Techniques
Powder X-ray diffraction analyses were performed using a
Philips 1140 diffractometer under the following conditions:
40 kV, 25 mA, CuKα (λ = 0.15406 nm) radiation. The samples,
as unoriented powders, were scanned in steps of 0.02◦ (2θ) in
the range from 2◦ to 70◦ at a speed of 2◦ per min.
Metal analyses were performed via inductively coupled
plasma–atomic emission spectroscopy by ALS Environmental,
Victoria, Australia.
Infrared experiments were carried out using an Equinox–IFS
55 spectrometer. Samples were mixed with KBr to produce a
disc with a 1% compound loading. The spectra were recorded
between 4000 and 400 cm−1 at a resolution of 2 cm−1 .
Table 3. Some properties of commercial dyes used in this work
Name Dye content Molecular mass εexp A λmax A
[%] [g mol−1 ] [M cm−1 ]
−1 [nm]
AB9 85 792.85 1.37 × 105 629
AY23 70 534.36 2.57 × 104 426
AR37 90 514.53 1.88 × 104 513
A From UV-visible spectral analysis.[24]
Adsorption of Ink-Jet Inks and Anionic Dyes
Surface morphologies and particle size were studied using
a Philips XL30 field emission scanning electron microscope
manufactured by Oxford Instruments operating at 5 kV.
Surface area, pore size, and pore volume were studied using
an ASAP 2010 Micromeritics instrument. The samples were
degassed at 378 K before analyzing using nitrogen adsorption–
desorption at 77 K.
The density was determined by helium pycnometry using an
AccuPyc 1330 gas-displacement pycnometer manufactured by
Micromeritics.
Adsorption Experiments
Mg-Al-LDH-NO3 materials were subjected to a dye affin-
ity test using purchased ink-jet inks according to published
methodology.[14] Ink-jet ink solutions (5 mL, 10% v/v in 20%
v/v glycerol/water solvent) were added to the pigment (0.5 g) in
a centrifuge tube. The tube was agitated using a vortex mixer
(2500 rpm) for 1 min followed by centrifugation (3000 rpm,
10 min, ambient temperature). The supernatant liquid was care-
fully removed and an aliquot (25 µL) was diluted with distilled
water (5 mL) and analyzed using a Varian Cary 300 Bio UV-
visible spectrophotometer. For materials that exhibited very high
affinity for the dye, a different dilution factor was used so that
the absorbance reading was in a measurable range.
For Mg-Al-LDH-NO3 materials (Mg:Al = 2.2 to 6.0) with
the best adsorption of ink-jet inks, adsorption isotherms were
determined for commercial dyes of known composition and
structure (approximate pH of measurement 7–8) as discussed
in previous publications.[14,23,24] Essentially, this involved using
a similar procedure as outlined in the adsorption experiments,
except that varying amounts of adsorbent materials were exposed
to a constant dye concentration.
Accessory Publication
The Accessory Publication contains basal spacings derived
from the XRD patterns (Table S1), N2 adsorption–desorption
isotherms (Fig. S1) and dye adsorption isotherms (Figs S2–
S5) for Mg-Al-LDH-NO3 with different Mg:Al ratios. The
Accessory Publication is on the Journal’s website.
Acknowledgements
The authors wish to thank the Smartprint Cooperative Research Centre,
Australia, for the financial support during the course of this study. A.R.A.
is also grateful to Monash Research Graduate School for a Postgraduate
Publication Award.
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