Available online at www.sciencedirect.

com

CERAMICS
INTERNATIONAL

Ceramics International 42 (2016) 774788

www.elsevier.com/locate/ceramint

Enhancement of optical properties and dependence of the crystal structure,

morphological properties of PrPO4 by microwave-assisted-hydrothermal
synthesis
D. Palma-Ramreza, M.A. Domnguez-Crespoa,n, A.M. Torres-Huertaa, E. Ramrez-Menesesb,
E. Rodrgueza, H. Dorantes-Rosalesc, N. Cayetano-Castrod
a

CICATA-Unidad Altamira, Instituto Politcnico Nacional, IPN, Km 14.5, Carretera Tampico-Puerto Industrial Altamira, C. P. 89600 Altamira, Tamps., Mxico
b
Universidad Iberoamericana, Departamento de Ingeniera y Ciencias Qumicas, Prolongacin Paseo de la Reforma 880, Lomas de Santa Fe C. P. 01219,
Mxico D.F, Mexico
c
Instituto Politcnico Nacional, ESIQIE, Departamento de Metalurgia, C. P. 07300 Mexico, D.F, Mxico
d
Instituto Politcnico Nacional, Centro de Nanociencias Micro y Nanotecnologas, Departamento de DRX, C. P. 07300 Mexico, D.F, Mxico
Received 24 June 2015; received in revised form 31 August 2015; accepted 1 September 2015
Available online 8 September 2015

Abstract
In this paper, PrPO4 nanostructures with hexagonal (rhabdophane phase) and monoclinic (monazite phase) structures were obtained by a
microwave-assisted-hydrothermal method and characterized by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Fourier
Transform Infrared Spectroscopy (FT-IR), Dynamic Light Scattering (DLS) and Reectance Diffuse Spectroscopy (DRS) and High Resolution
Transmission Electron Microscopy (HRTEM). A rst study of the experiment was done in order to evaluate the reaction time (130 and 180 1C),
synthesis time (15 and 30 min) and sintering temperature (400 and 600 1C). Subsequently, the medium pH was adjusted to 1, 3, 5, 9 and 11 under
two previously selected conditions. The results highlight the signicant effects exerted by the synthesis parameters on the structure, crystal and
particle sizes, morphology type, reaction mechanism as well as on the PrPO4 absorption/transmission region.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: Praseodymium phosphate; Microwave-assisted-hydrothermal synthesis; Nanorod-like morphologies; Optical properties

1. Introduction
Rare-earth phosphates have ideal characteristics to be used
in uorescent lighting, uorescent hosts, scintillators and laser
devices as single crystals, powder and glass [1,2]. Phosphors
consist of a host lattice with a luminescent ion which has the
ability to convert short wavelength radiation into mostly lower
energy radiation in the visible (VIS) range [3]. The synthesis to
obtain activated phosphate particles and further embedded in
different polymer matrix has been used to obtain structures as
waveguides, photonic crystals, coatings, biomedical diagnostic, energy conversion, telecommunications and bulk glasses
n

Corresponding author.
E-mail address: mdominguezc@ipn.mx (M.A. Domnguez-Crespo).

http://dx.doi.org/10.1016/j.ceramint.2015.09.002
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

including spheres, rings and other geometries exploited in

optical resonators fabrication [36]. In particular, nanoparticles
of praseodymium phosphate have been hardly studied and their
optical properties can be of interest, e. g., as UV absorbers in
plastics, either to conserve the structural properties from
degradation by UV light, or in the form of composites which
protect UV sensitive materials [7]. It has been stated that in
these industrial applications, the synthesis method of PrPO4
plays an important role in the production of nanostructures
with a specic morphology [8]. A lot of effort has gone into
synthesizing monazite (monoclinic structure) and rhabdophane
(hexagonal phase) rare-earth phosphates under different parameters and methods (e. g, hydrothermal, solgel, wet-chemical
and high-temperature-solidsolid reaction methods) [3,9,10];
however, these methods have noticeable disadvantages. Firstly,

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

775

in order to increase and improve the synthesis rate, their

chemical homogeneity and morphology, the initial solutions
are heated up under elevated pressure and temperatures
(hydrothermal method), which results in segregation due to
the solubility differences in the individual components [8]. It
also requires long reaction times of about 4 [2] to 12 h [11],
even 40 days when the compounds are obtained at room
temperature [10] as well as a large quantity of reactants are
required for the synthesis [3,8]. More recently, the ongoing
microwave assisted hydrothermal method was proved to be a
green approach for synthesizing nanomaterials which have
some advantages over the conventional hydrothermal method
such as the requiring of lower synthesis temperatures to reach
the complete reaction and shorter reaction times [12,13].
However, to the best of our knowledge, the study on tailored
PrPO4 nanostructures by microwave-assisted-hydrothermal
synthesis has yet to be investigated. Herein, we propose a fast
synthesis to obtain PrPO4 nanostructures with varied morphologies and structures through a microwave-assisted-hydrothermal approach. The evolution from nanorod-like to sphericallike morphologies was modulated by simply changing the pH
in the aqueous solution. Additionally, the dependence of the
optical and morphological properties of the as-prepared PrPO4
materials on the solution pH is also discussed. The process was
fast and reproducible in comparison with other conventional
techniques like solgel.

synthesis was assisted by microwave energy using a microwave

oven manufactured by CEM Corporation. The experiment was
carried out as follows: 50 mL of Pr(NO3)3  6H2O (0.10 mol)
(Sigma-Aldrich, 99% purity) were added dropwise to 25 mL of a
tripolyphosphoric acid solution (0.035 mol  1, H5P3O10) previously prepared from the ion exchange of sodium tripolyphosphate Na5P3O10  5H2O (pure p.a., Z98.0% (T), Sigma-Aldrich)
using a cation exchange resin (Dowex 50 W X4 100200 mesh),
then deionized water was added to adjust a nal volume of
100 mL. The pH of the nal solution was  2.2. The solutions
were transferred into a container (HP-500 vessel from CEM
Corporation). The autoclave was sealed and introduced into the
oven (Frequency 2.45 GHz, power of  200 W) which has an
attached pressure sensor and inserted ber optic temperature
sensor.
An initial set of experiments (see Table 1) was prepared to
assess the optimal conditions by varying the reaction temperature, synthesis time and sintering temperature (Tr, t, and Ts,
respectively). Once the initial set of experiments was completed, the conditions labeled as 4 and 8 were selected to
establish the pH at which the monoclinic phase could be
favored at lower sintering temperatures (400 and 600 1C) in
comparison with the traditional process where a temperature
above 800 1C is required [9]. The pH values were adjusted
using NH4OH (30%) and HNO3 (37%) to reach pH values of
1, 3, 5, 9 and 11 for each condition.

2. Experimental procedure

2.1. Characterization of nanopowders

PrPO4 powders were evaluated by X-ray powder diffraction
(XRD) using a Bruker D8 Advance diffractometer equipped
with Lynxeye detector and Cu K radiation ( 1.5405 ) at
35 kV and 25 mA. The data were recorded at room temperature
in the 2 range of 15701, step size of 0.0161 and step time
of 0.5 s.

The synthesis experiment for PrPO4 powders was done by

modifying an earlier hydrothermal method reported by Juliana
et al. for the synthesis of CePO4 [14]. Ce3 has similar ionic
radius and 4f shell conguration as Pr3 , so the same behavior
would be expected in the synthesis of PrPO4. The hydrothermal

Table 1
Set of experiments for the synthesis of PrPO4 displaying the phase composition and synthesis parameters.
Experiment

1
2
3
4
5
6
7
8
4
4
4
4
4
8
8
8
8
8

pH

1
3
5
9
11
1
3
5
9
11

Reaction temperature (Tr, 1C)

130
180
130
180
130
180
130
180
180

Synthesis time (t, min)

15
15
30
30
15
15
30
30
30

Sintering temperature (Ts, 1C)

400
400
400
400
600
600
600
600
400

600

Phase composition (wt%)

Monazite

Rhabdobphane

19.95
58.74
47.69
69.64
100
100
92.92
100
94.68
60.26
73.8
82.75
86.45
100
98.15
100
99.75
100

80.05
41.26
52.31
30.36
0.0
0.0
7.08
0.0
5.32
39.74
26.2
17.25
13.55
0.0
1.85
0.0
0.25
0.0

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

PDI =

20

Dw
Dn

where ni is the number of CePO4 nanoparticles with

diameter Di.
Diffuse reectance of the samples was evaluated by Ultravioletvisible diffuse reectance spectroscopy (UVvis DR)
using a 110-mm-diameter-integrating sphere accessory
mounted on a Cary 5000 Spectrophotometer.
The uorescence intensity measurements were performed
using a Carl ZEISS Microscope, LSM 700 confocal microscope
and the built software ZEN of the LSM 710. The emission
spectra were acquired at 405 nm and room temperature.

3. Results and discussions

The crystallization process of PrPO4 powders was investigated by the X-ray diffraction technique. The XRD patterns of
PrPO4 samples before and after being thermally treated at 400
and 600 1C (pH 2.2) are shown in Fig. 1a and b. The
obtained patterns can be indexed to the hexagonal and
monoclinic phases of the praseodymium phosphate hydrate
known as rhabdophane (PrPO4  H2O, a b 7.0 , c 6.43
, ICDD 00-020-0966) and praseodymium phosphate known
as monazite (PrPO4, a 6.434 , b 6.760 , c 6.982 ,
ICDD 01-083-0653). In general, non-signicant changes in the

(241)

(003)

(112)

(102)

(202)

(200)

(211)
(103)
(300)
(301)
(103)
(203)
(302)
(140)
50

t
180C 30min

60

70

T r180C t30min T s600C

T r130C t30min T s600C
Monoclinic

(241)

(114)
(014)

(031)
(311)
(212)
(231)
(103)
(023)
(322)
(132)
(140)

T r130C t15min T s600C

(202)
(112)

(111)
(200)
(120)
(012)

T r180C t15min T s600C

T r180C t30min T s400C

T r130C t30min T s400C

30

(203)
(302)

(301)

40

50

(003)

T r180C t15min T s400C

T r130C t15min T s400C

Hexagonal

20

(4 )

40

(211)
(003)

(3 )

30

Tr

2 (degrees)

niDi 5

(020)

(101)

T r180C t15min

(112)

niDi

(2 )

T r130C t 30min

(200)
(102)

Dz =

niDi 4
niDi 3

t
r130C 15min

Hexagonal

(101)

Dw =

(1 )

Monoclinic

(101)
(110)
(111)

niDi
Dn =
ni

Intensity (a. u.)

Morphology and texture of nanopowders were examined by

high resolution scanning electron microscopy (HRSEM/EDS)
using a JEOL JSM-6701F equipment. Transmission electron
microscopy (TEM) micrographs were obtained with a JEMARM200CF, JEOL, (Lattice resolution 78 picometers, acceleration voltage 200 kV).
FT-IR (Fourier Transform Infrared Spectroscopy) spectra
were recorded on a spectrum one Perkin Elmer spectrometer
(4 cm  1 of resolution setting) in order to evaluate the
vibrational properties of the PrPO4 bands. Samples were
scanned at least 40 times in the range of 1500450 cm  1 by
using KBr pellets.
Particle sizes were measured in a Malver Zetasizer Nano
ZSP, model ZEN5600 equipped with an Argon laser ( 633
nm) at room temperature. Previously, PrPO4 powders were
diluted with water in a 1/100 ratio. Data were calculated from
the particle diameter moments (number-average diameter Dn;
weight-average diameter Dw and z-average diameter Dz), using
Eqs. (1)(4) and the polydispersity index (PDI) was also
determined as follows:

Intensity (a. u.)

776

60

70

2 (Degrees)
Fig. 1. X-ray diffraction patterns of: (a) non-sintered PrPO4 powders obtained
under the conditions mentioned in Table 1, (b) PrPO4 powders sintered at two
different temperatures (400 and 600 1C).

structural phases were observed by varying either the reaction

temperature (from 130 to 180 1C) or reaction time (15 and
30 min), Fig. 1a. The resulting patterns reveal that a mixture of
phases (mainly rhabdophane) is obtained with the proposed
synthesis approach. It has been stated that the crystal structure
belonging to the hexagonal system (named rhabdophane in the
case of the light lanthanide orthophosphates, Ce3 , Ln3 and
Pr3 ) requires calcination temperatures above 800 1C to
transform it into monazite [9]. However, we found in this
work that such phase transformation can take place at lower
temperatures (130 and 180 1C) when the rare earth phosphate
(PrPO4) is synthesized by the microwave-assisted-hydrothermal method.
Commonly, rhabdophane is a very stable structure and of
particular interest in tribological applications [15], whereas the
monazite phase has been reported to be used in tribological
applications too, it can display a high optical emissivity
accompanied by a high fusion temperature [16] and recently,
this structure has shown interesting properties as UV absorber
in plastics.

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

Thus, to obtain a high percentage of the monoclinic

structure, the samples were thermally treated from 400 to
800 1C. During the XRD measurements, however, non-important changes were observed with the sintering temperatures up
to 600 1C. The as-treated samples at 400 and 600 1C and the
XRD patterns are shown in Fig. 1b. The XRD patterns of the
samples sintered at 400 1C are mainly composed of the
monoclinic phase (58.74 and 69.64 wt%) when a reaction
temperature of 180 1C is applied during the synthesis. As the
sintering temperature is increased from 400 to 6001 C, several
peaks of the hexagonal phase tend to shift to lower 2 angles,
indicating the transformation to the monoclinic phase (ICDD
01-083-0653), Table 1.
A quantitative estimation of the domain size for PrPO4
nanopowders was evaluated from the three most intense peaks
using the Scherrer modied equation developed by A. Monshi
et al. [17]. The method assumes that there are N peaks of
specic nanocrystals which must present identical L values in
the range of 01801 (2) or 0901 (), assumption that is not
necessarily true and consequently, the mathematically errors in
the calculation must be decreased by using the least squares
method to obtain the following equations:
=

K
K 1
=
L. cos
L cos

In = In

K
K
1
= In
+ In
L. cos
L
cos

(5 )

(6 )

After applying the least squares method, the slope calculated

from the In vs In(1/ cos ) plot and a In(K / L ) intercept can
be obtained using the following expression [17].
eIn

K
L

K
L

(7 )

For the calculations, a K value of 0.94 was considered since

the shape morphology of the obtained PrPO4 has been reported
as rods [18] and the corresponding data are shown in Table 2.
The crystallite size seems to be very stable in the 1st set of
experiments even before the sintering process (1013 nm).
Under these conditions, the sintering temperature has not great
inuence on the crystallite size.
The molecular vibration of the as-prepared PrPO4 nanopowders was investigated using Fourier Transform Infrared
(FT-IR) Spectroscopy, Fig. 2a and b. The spectra displayed the
characteristic bands c.a. 956 cm  1 and 618 cm  1, 567 cm  1
and 541 cm  1 which correspond to the bending ( v4 ) and
stretching ( v3) vibrations of PO3
4 , respectively [1921],
however, the intensity of the bands and additional bands
emerging in the analysis highlight that the synthesis time
exerts a great inuence on the formation of bonds. For
example, the sample synthesized at 180 1C and 15 min is
similar to those obtained at 130 1C (with 15 or 30 min),
whereas if the time is increased to 30 min at the same synthesis
temperature, a new vibrational band appears at 578 cm  1. This
band is probably related to the structural re-arrangement of
PrPO4 since it is found in all the samples sintered at 600 1C

777

Table 2
Crystal size of PrPO4 and treatment of linear plots to obtain the crystallite size
from Scherrer modied equation.
Experiment pH As-prepared

eln
1
2
3
4
5
6
7
8
4
4
4
4
4
8
8
8
8
8

K / L

0.01372
0.01235
0.0116
0.0122
0.01372
0.01235
0.0116
0.0122
1 0.0074
3 0.0118
5 0.0103
9 0.0028
11 0.0035
1 0.0074
3 0.0118
5 0.0103
9 0.0028
11 0.0035

L (nm) Sintered

0.94x 0.154051
L

eln
11
12
12
12
11
12
12
12
18
12
13
48
39
18
12
13
48
39

K / L

0.0148
0.0116
0.0110
0.0123
0.0003
0.0012
0.0007
0.0004
0.0218
0.0119
0.0115
0.0628
0.0410
0.0511
0.0096
0.0187
0.0108
0.0060

L (nm)
0.94x 0.154051
L

10
12
13
12
11
12
12
12
7
11
12
3
3
3
12
12
13
23

(Fig. 2b). Another relevant characteristic observed in this work

is that by increasing the sintering temperature from 400 to
600 1C, the signal at 956 cm  1 becomes sharper as the
temperature is increased and it is related to the vibration of
the PO bond in the monoclinic structure [22].
The particle size distribution graphs, the average particle
size (Dz), and polydispersity index (PDI) of the PrPO4 powders
are shown in Fig. 3 and Table 3. The results in Table 3 show
that the mean average sizes (Dz) from DLS measurements for
the as-obtained PrPO4 nanostructures range from 324 to
867 nm. However, the expected PDI was found to be above
1.5, suggesting that the PrPO4 nanoparticles are mostly
composed of multiple particle populations, i.e., poly-dispersed
systems of particles [23].
The morphology of the as-prepared samples is shown in
Fig. 4. It is noticeable that agglomerates of rod-like and semispherical particles were formed independently of the synthesis
conditions. The nanorod morphology has been reported to be
obtained during the synthesis of PrPO4 [11]. These nanorods
tend to stack and agglomerate to each other forming larger
particles. It was not possible to measure with accuracy the
length and diameter of the rods; however, a preliminary
estimation of the length and diameter is about  200 nm and
 25 nm, respectively.
Results of different syntheses have shown that pH is a
signicant parameter in altering morphology [24]. During the
rst set of experiments, the synthesis pH was maintained
constant to evaluate morphology changes. For this reason and
in order to obtain more information on the pH effect on the
morphology and properties, two conditions were selected to
evaluate the dependency on the acid or alkaline initial solution
as well as the sintering temperature. Previously, it has been
found for CePO4 that by pH modulating, it is possible to obtain
a monoclinic structure at low sintering temperatures. Thus, the

778

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

100

Transmittance (%)

Transmittance (%)

100
80
60
40
20
0

Transmittance (%)

1200

1000

800

40
20

600

100

100

80

80

60

60

40

40

20

20

1400

1200

1000

800

600

1400

1200

1000

800

600

1400

1200

1000

800

600

1400

1200

1000

800

600

0
1400

1200

1000

800

600

100

Transmittance (%)

100

Transmittance (%)

60

0
1400

80
60
40
20
0

80
60
40
20
0

1400

1200

1000

800

600

100

Transmittance (%)

100

Transmittance (%)

80

80
60
40
20
0

80
60
40
20
0

1400

1200

1000

800

600

Fig. 2. FT-IR spectra of the PrPO4 nanopowders sintered at: (a) 400 1C, and (b) 600 1C under the conditions of the rst set of experiments.

conditions of experiments 4 and 8, constant reaction temperature (Tr 180 1C) and time (30 min) were selected. During
these experiments, pH was adjusted at 1, 3, 5, 9 and 11, using
two sintering temperatures (400 and 600 1C); the experimental
matrix is also presented in Table 1.
Structural dependence of the solution pH was investigated
for these experiments. The pH effect on the structural vibrations was characterized for these experiments and the results
are shown in Fig. 5a and b. The spectra display the

characteristic bending (at 957 cm  1) and stretching (at 615,

580, 566 and 542 cm  1) vibrations of PO3
4 , which are more
pronounced as pH goes from alkaline to acid medium. The
most notable difference by adjusting the pH is that the band at
615 cm  1 is slightly shifted to lower wavenumbers and the
region between 1200 and 1000 cm  1 is well dened as the
sintering temperature is increased to 600 1C (Fig. 5a and b).
The XRD patterns of the samples obtained at different pH
values are presented in Fig. 6ac. The analyzes of the XRD

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

Frequency

20
15

Tr180t15Ts400

25

Tr180t15Ts400

Dz = 648
PDI = 1.6

20

Dz = 867
PDI = 4.2

Frequency

25

10
5

15
10
5
0

0
0

200

400

600

800

1000

200

Diameter (nm)
35

Dz = 324
PDI = 3.8

20

600

35

800

1000

Tr180t30Ts400

30

Dz = 851
PDI = 2.5

25

Frequency

Frequency

25

400

Diameter (nm)

Tr130t30Ts400

30

15
10
5

20
15
10
5

0
0

100

200

300

400

500

600

Diameter (nm)

200

400

600

800

1000

Diameter (nm)

40

Tr130t15Ts600

30

Dz = 377
PDI = 4.4

35

Tr180t15Ts600

30

Dz = 462
PDI = 3.5

25

Frequency

Frequency

779

20
10

20
15
10
5

100

200

300

400

500

600

Diameter (nm)
30

Diameter (nm)

Tr130t30Ts600

30

Tr180t30Ts600

25

Dz = 433
PDI = 4.0

Dz = 617
PDI = 3.7

15
10
5

Frequency

Frequency

25
20

100 200 300 400 500 600 700 800

20
15
10
5

200

400

600

800

1000

Diameter (nm)

100 200 300 400 500 600 700

Diameter (nm)

Fig. 3. Particle size distribution of the 1st experiment particles sintered at 400 and 600 1C.

patterns of the as-prepared PrPO4 (Fig. 6a) show a clear pH

dependence of the PrPO4 nal structure. It is easy to perceive
that by using pH 1, a percent of the monoclinic phase can be
reached without requiring sintering temperatures, where other
pH conditions favored a phase mixture of the monoclinic/
hexagonal (pH 35) and monoclinic/hexagonal structures
with small reections emerging from the tetragonal phase at
pH 911 (PDF #00-033-1077).
In the case of the samples synthesized under experiment
4 conditions and sintered at 400 1C (Fig. 6b), the XRD patterns
showed that the characteristic reections of both phases still
persist within the evaluated pH interval. However, at low pH, a

high percentage of the monazite structure (94.68 wt%) is

favored; whereas these concentrations decrease and slightly
increase as pH goes from 3 to 5 (see Table 1). It was observed
that a high percentage can be reached by increasing the
solution pH. On the other hand, samples thermally treated at
600 1C displayed XRD peaks that matched predominantly well
with the monazite structure, Table 2. Using this sintering
temperature, the monazite structure is reached independently
of the solution pH (Fig. 6c).
The pH inuence on the PrPO4 crystal size was also
calculated through the Scherrer modied equation. During
the second stage of experiments (4 and 8), the crystallite size

780

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

tended to increase with pH from 12 to 48 nm, but it got

reduced in the 323 nm interval with the sintering process
(Table 2). The pH inuence can be divided into three aspects:
(i) the crystal size in acid medium (pH 1) displays a decrease
after 400 1C, (ii) at intermediate acid character (pH 35) the
size is almost stable and it is similar to one obtained in the rst
set of experiments at pH 2 and (iii) at higher pH values (9
and 11), the crystal size tends to decrease with the sintering
temperature. A similar trend to reduce the crystal size with pH
Table 3
Z-average particle diameter (Dz) and polydispersity index (PDI) of PrPO4
nanopowders.
Condition no.

Dz(nm)

PDI

1
2
3
4

648
867
324
pH1 (885)
pH2 (851)
pH3 (724)
pH5 (417)
pH9 (756)
pH11 (528)
377
462
617
pH1 (338)
pH2 (433)
pH3 (273)
pH5 (287)
pH9 (615)
pH11 (799)

1.6
4.2
3.8
pH1 (1.0)
pH2 (2.5)
pH3 (1.3)
pH5 (2.4)
pH9 (4.4)
pH11 (2.0)
4.4
3.5
3.7
pH1 (1.8)
pH2 (4.0)
pH3 (1.5)
pH5 (1.3)
pH9 (1.2)
pH11 (1.1)

5
6
7
8

Tr130,t15,Ts400

100 nm

Tr130,t15,Ts600

100 nm

Tr180,t15,Ts400

100 nm

Tr180,t15,Ts600

100 nm

has been reported during the synthesis of LaPO4 nanopowders

[25]. It is well known that the microwave-assisted-hydrothermal method reduces the activation energy of the materials, thus
lowering the synthesis temperatures of the materials, as
compared with the conventional ceramic method [26]. Therefore, the microwave-assisted-hydrothermal method along with
an adequate choice of the synthesis parameters can help to
modulate the structural phases during the synthesis of PrPO4
nanoparticles.
To corroborate our assumption regarding the dependence of
the structure, phase composition and particle sizes on pH,
HRTEM measurements were carried out. HRTEM and Fourier
Transform-Filtered Images (inset) of samples prepared under
the conditions of experiments 4 (Tr180t30Ts400) and 8
(Tr180t30Ts600) at different pH values are presented in
Figs. 7 and 8, respectively.
The HRTEM images proved that the nanoparticles are
composed of two types of morphologies: rods and spherical
nanoparticles, which are quite dependent of the pH in the
reaction medium. As expected, the nal products synthesized
at pH 1 consist mainly of long rods whose length is affected by
the sintering temperature; powders thermally treated at 400 1C
showed diameters (D) between 12 and 30 nm with lengths (L)
ranging from 100 to 350 nm, whereas at 600 1C, shorter
nanorods were obtained (D 1026 nm, L 40200 nm). It
is also clearly seen that by increasing the pH at 3, the nanorods
start evolving to shorter and narrower sizes with lengths c.a.
20173 nm (sintered at 400 1C) and up to 1547 nm (sintered
at 600 1C). Upon rising to pH 5, the length appearance is more
evident since the analysis of the micrographs showed particle
sizes between 7 and 50 nm, independently of the sintering

Tr130,t30,Ts400

100 nm

Tr130,t30,Ts600

100 nm

Tr180,t30,Ts400

100 nm

Tr180,t30,Ts600

100 nm

Fig. 4. SEM micrographs of the 1st set of experiments: (a) Tr130t15Ts400, (b) Tr180t15Ts400, (c) Tr130t30Ts400, (d) Tr180t30Ts400, (e) Tr130t15Ts600, (f) Tr180t15Ts600,
(g) Tr130t30Ts600 (g), and (h) Tr180t30Ts600.

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

conditions. By further increasing the pH up to alkaline

medium, a further decrease in morphology from nanorods to
spherical particles was provoked.
The interplanar spacing of the PrPO4 crystals was determined from the inverse Fourier Transform of the HRTEM
micrographs. It is clearly seen that at pHs 1 and 3, the sample
synthesized under no. 4 conditions (sintered at 400 1C) shows
a fringe spacing value between 6.2 and 6.8 , which matches
to the theoretical value of (100) of the hexagonal PrPO4,
indicating that the growth direction is parallel to it (Fig. 7).
This fringe value persists in the samples that were synthesized

t T
r180 30 s400

pH 1

580 566

Transmittance (%)

pH 3
542

996 957

pH 5

615

pH 9

pH 11

1400

1200

1000

800

600

-1

Wavelength (cm )

t T
r180 30 s600

pH 1

580

Transmittance (%)

pH 3

566

957
614 539

pH 5

pH 9

pH 11

1400

1200

1000

800

600

-1

Wavelength (cm )
Fig. 5. FT-IR spectra of the PrPO4 nanopowders: (a) samples synthesized
under experiment 4 conditions at different pH values and (b) samples
synthesized under experiment 8 conditions at different pH values.

781

at pH 5. Different crystals belonging to the monoclinic system

), (002) and
at (100) (d 3.9 ) plane are also seen. Planes (111
(020) are evident in the spherical particles synthesized in
alkaline medium.
On the other hand, when samples are sintered at 600 1C
(condition no. 8), the monoclinic fringe space is more evident
independently of the morphology type: nanorods or spherical
particles (Fig. 8).
The monodispersity analysis of the PrPO4 synthesized under
these experimental conditions showed a strong dependence of
the particle size and shape on the pH and sintering temperature. The PDI values for the Tr180t30Ts400 samples show
monodisperse particles in acid medium (pH 13), however,
the sintering temperature modies the particle size distribution
as it is shown by the samples prepared at Tr180t30Ts600. In the
last case, only at pH between 5 and 11 monodisperse systems
can be obtained. The particle size estimated by DLS was
compared with TEM images, which are inset in the particle
size distribution graphs in Figs. 9 and 10. In agreement with
the TEM micrographs, the highest particle size, estimated by
DLS, is caused by nanopowder agglomeration. In fact, with
exception of the samples obtained under the Tr180t30Ts400
(pH 1) conditions, where nanorods are seen (23 nm dia.
and 94 nm length on average), all the samples tend to form
agglomerates.
The synthesis of PrPO4 by the hydrothermal method is
associated with the interaction of the dipole molecules with
high frequency electromagnetic radiation. However, when it is
assisted by the microwave method, a microwave diffuses
volumetrically through the material being heated; in such
way, the polar molecules (such as H2O) absorb microwave
energy and provoke energetic rotational movements as a
consequence of the polarization of ions [13], providing a
platform to reduce the synthesis time and control the nucleation and growth of PrPO4 nanostructures. It has been stated
that some rare earth ions like La3 and PO3
4 are stacked
alternately along the [001] direction in the hexagonal crystal
structure of LaPO4; thus, it is reasonable to expect the
praseodymium ion to be of similar ionic radii and the charge
must display a comparable behavior at low pH. It is believed
that the highest H ion concentration produces the adhesion of
these ions on the crystal facets, producing an increase in the
electrostatic potential and allowing the union of the spherical
particles to form the nanorod-type morphology as it is shown
in Fig. 11. In these systems, the largest particles grew at the
cost of the small ones, due to the solubility energy difference
between the largest particles and the smallest ones, according
to the well-known ThomsonGibb law [27]. Thus, the stacking
leads to an amount of net charges and the strongest polarity for
(100) facets in comparison with other lattice planes. In such
case, the activation energy for crystal growth along the c axis
of the hexagonal phase is lower than that perpendicular to the c
axis from a thermodynamic perspective, which implies that the
growth rate along the c axis is higher than that perpendicular to
the c axis. All these affecting factors drive 1D nanorods to
grow preferentially along the [100] direction. Consequently,
the promotion of the anisotropic growth of the as-prepared

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

Monoclinic

40

50

60

70

20

40

50

(4 0 0 )

t
T
r180C 30min s400 pH1

(1 3 2 )

(3 0 1 )
(1 0 3 )

(3 1 1 )

30

t
T
r180C 30min s400 pH3

(3 2 2 )

(1 0 3 )

(1 1 2 )

(1 0 2 )

t
T
r180C 30min s400 pH5

(0 1 2 )

(0 2 0 )

(0 0 2 )

t
r180C 30min pH1

(011)
(111)
(020)
(200)
(120)
(012)
(202)
(112)
(031)
(103)
(212)
(231)
(103)
(023)
(322)
(132)

Hexagonal

(340)

Monoclinic

t
T
r180C 30min s400 pH9

(1 0 1 )

In te n s ity (a .u .)

(033)

T
t
r180C 30min pH3

(323)

(112)
(211)

(101)

Hexagonal

30

11

t
r180C 30min pH5

(301)
(320)
(203)
(302)

(200)
(102)

20

T
t
T
r180C 30min s400 pH11

Tr180Ct30min pH
9

(140)
(004)
(014)
(014)

(311)

(120)

(112)

(200)

Tr180Ct30min pH

(103)

Intensity (a.u.)

(120)

*Tetragonal

(311)
(024)

782

60

70

2 (Degrees)

2 (degrees)

Tr180Ct30minTs600 pH

(431)

(111)

Intensity (a.u.)

(120)

(002)

(002)

T
t
T
r180C 30min s600 pH9

20

t
T
r180C 30min s600 pH5

t
T
r180C 30min s600 pH3

T
t
T
r180C 30min s600 pH1

(202)
(112)
(122)
(031)
(103)
(212)
(231)
(103)
(023)
(322)
(132)
(140)
(004)
(014)
(124)

(111)
(020)
(200)
(002)
(012)

(110)

Monoclinic

11

30

40

50

60

70

2 (degrees)
Fig. 6. X-ray diffraction patterns of PrPO4 samples: (a) as-prepared samples adjusted at different pH values, (b) samples synthesized under experiment 4 conditions
at different pH values and (c) samples synthesized under experiment 8 conditions at different pH values.

nanorods (100) is mainly governed by a general cooperative

effect including the intrinsic structural features of specic
faces, local solution details, foreign energy activation and
autogenous pressure [28].
On the other hand, when increasing the pH value, a semispherical-type morphology is favored. According to previous works
related to rare earth phosphates, colloidal precipitates have been
observed as the pH value of the solution was decreased [29].
However, in this work, precipitates were more evident in alkaline
than in acid medium. The precipitates were associated with the

presence of a small amount of free PO3

4 ions, where the motion
speed reached a maximum value [29].
During the synthesis of PrPO4, nucleuses of tiny crystals are
formed and subsequently the crystal grows generating the
semispherical particles. There are higher OH  ion concentrations which are absorbed onto the crystal facets, producing a
double layer composed of cations (H and NH4 ) and anions
(NO-3 and OH  ) as shown in Fig. 11.
By taking into account these facts and considering those
already established in the literature [15,29], the most probable

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

reactions of the PrPO4 formation, either in acid or alkaline

solutions, can be proposed as follows:
Reaction in acid medium:
H 5P3O10(aq) + H 2O (aq) H4P2O7(aq) + H 3PO4(aq)

(8 )

H4P2O7 + H 2O 2H 3PO4

(9 )

783

Pr(NO3)3 (aq)6H 2O + HNO3 (aq) + H 3PO4(aq)

PrPO4(s) + 4HNO3(aq) + nH 2O(aq)

(10)

Reaction in alkaline medium:

H 5P3O10(aq) + H 2O (aq) H4P2O7(aq) + H 3PO4(aq) (11)

Fig. 7. Selected HRTEM micrographs of experiment 4 at different pH values.

784

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

Fig. 8. Selected HRTEM micrographs of experiment 8 at different pH values.

H4P2O7 + H 2O 2H 3PO4

(12)

Pr(NO3)3(aq)6H 2O(aq) + NH4OH(aq) + H 3PO4(aq)

PrPO4(s) + 2NH4NO3(aq) + nH 2O(aq)

(13)

The effect of the reaction temperature, synthesis time and

sintering temperature used for obtaining PrPO4 on the optical
properties was evaluated from the diffuse reectance spectra

and the results are presented in Fig. 12. It can be clearly

observed that the spectra consist mainly of four strong bands at
445, 472, 484, 595 and 601 nm assigned to 4f4d transitions
of the following energy levels: 3H4-3P2, 3H4-3P1,
3
H4-3P0, 3H4-3D2 (upper) and 3H4-3D2 (lower), respectively [30]. All the spectra display absorption in the UV range,
indicating that they are good candidates as UV absorbers to be
used in polymer applications, where degradation is needed to
be prevented. The only remarkable difference is found for the

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

785

Fig. 9. Particle size distribution of samples synthesized under experiment 4 conditions at different pH values.

powders synthesized at pH 9 and 11, which display absorption

from the UV region to the visible range; however, these
nanopowders can also be used for polymer applications since
the absorption in the visible range does not affect the
macromolecular backbone. From the absorption spectrum
and KubelkaMunk function, it was found that the band gap
varies from 5.1 to 5.4 eV with small variations depending on
the solution pH.
To correlate the optical properties with the nal application,
the uorescence of selected samples was acquired using a
ZEISS LSM700 confocal microscope.Fig. 13 displays the
emission spectra of selected PrPO4nanoparticles samples under
405 nm of excitation at room temperature. Comparison of the
emission spectrum of Tr1801Ct30minTs6001C modied in acid
conditions with that obtained in alkaline media afforded the
high association of the pH with the morphological properties
and the nal photonic properties of PrPO4nanostructures.
Comparing the two emission spectra, it can be found that
PrPO4 nanorods (i.e. sample obtained at pH 1) spectrum
consists mainly of two separated bands of uorescence with
maxima at  510 nm and  610 nm which are due to the
3
P0-3H5 and 1D2-3H4 transitions of Pr3 in the sample
[31]. Results reveal no signicant dependence of emission on

the sintering temperature. In the case of smaller particles

(obtained at pH 9), it is seen that an enhancement in OH 
ions during the powders synthesis could lead to the quenching
of the luminescence; which may explain the poor emission of
prepared samples at pH 9.
Typically semi-conductor material used as UV absorber
works by absorbing photons producing electronhole pairs
which in turn react with oxygen, water or hydroxyls groups to
form free radicals when holes and electrons join the surface
starting the breaking bonds in the polymer [32], because the
latter will degrade more easily the backbone as a consequence
to the heat concentrated on them. Thus, the results highlight
that microwave-assisted hydrothermal method can modulate
crystallite size, structure and morphology of UV absorbers
materials, offering the possibility to transform the high energy
from UV photons on radiation of low energy (Visible light)
instead of concentrating the energy (thermal energy). The latter
is of great advantage to avoid plastic degradation.
4. Conclusions
Polycrystalline PrPO4 nanostructures were successfully prepared by the microwave-assisted-hydrothermal method from Pr

786

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

25
20

15

Frequency

Frequency

20

10
5

15
10
5
0

100

200

300

400

500

Diameter (nm)
30
25
20

20

Frequency

Frequency

25

15
10

15
10
5

0
0

100

200

300

400

Diameter (nm)

500

600

200

400

600

800

1000

Diameter (nm)

25

Frequency

20
15
10
5
0
0

200

400

600

800

1000

Diameter (nm)
Fig. 10. Particle size distribution of samples synthesized under experiment 8 conditions at different pH values.

Fig. 11. Schematic representation of the formation of PrPO4 with (a) nanorod-type morphology in acid medium and (b) semispherical-type morphology in alkaline
medium at crystal level.

(NO3)3  6H2O and a tripolyphosphoric acid solution. The

method was simple and easily repeated and could be developed for the synthesis of different rare earth phosphate

materials. The study also demonstrates that by using this

method and modulating the pH, the hexagonal structure is
transformed into the monoclinic one. Even this transformation

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

Tr
t
Ts
Tr180Ct15minTs600C 180C 30min 400C

100

Tr130Ct30minTs400C
Tr130Ct15minTs600C

787

4 (Tr180Ct30minTs400C)
8 (Tr180Ct30minTs600C)

8 (pH 3)

100

8 (pH 1)

Diffuse reflectance (%)

D iffuse reflectance (% )

4 (pH 5)

80

60

Tr130Ct15minTs400C
Tr180Ct30min

40

Tr180Ct30minTs600C

Tr130Ct30min

Tr130Ct30minTs600C
Tr180Ct15minTs400C

Tr130Ct15min

20

Tr180Ct15min

80

4 (pH 3)

60
4 (pH 1)
8 (pH 5)

40

8 (pH 9)

20

4 (pH 11)

8 (pH 11)

4 (pH 9)

0
200

300

400

500

600

700

200

300

400

500

600

700

(nm)

(nm)

Fig. 12. Diffuse reectance spectra of: (a) the entire as-prepared PrPO4 powders before and after the sintering process (1st experiment) and (b) powders synthesized
under conditions 4 and 8 and adjusted at different pH values.

160

Tr180Ct30minTs600C pH 1
140

Tr180Ct30minTs600C pH 9

510 nm
Emission Intensity

120

are also grateful for the nancial support provided by CONACYT through the CB2009-132660 and CB2009-133618
projects and to IPN through the SIP 2015-0202 and 20150227 projects and SNI-CONACYT.

Tr180Ct30minTs400C pH 1

100

References

80

610 nm

60
40
20
0
450

500

550

600

650

Emission wavelength [nm]

Fig. 13. Fluorescence of selected PrPO4 samples under 405 nm excitation.

took place at lower temperatures in comparison with other

traditional processes such as the solid state reaction, coprecipitation, solvothermal or solgel techniques.
The size and shape of the as-obtained nanopowders were
strongly dependent on the pH, which can be the most
determining parameter during the synthesis process. Finally,
the results regarding the PrPO4 optical properties reveal the
high absorption in the UV region, indicating the possible
application of these materials to reinforce the structural
properties of polymeric materials.
Acknowledgments
D. Palma-Ramrez is grateful for her postgraduate scholarship to CONACYT, SIP-IPN and COFAA-IPN. The authors

[1] A. Jouini, M. Ferid, J.-C. Gcon, L. Grosvalet, A. Thozet, M. TrabelsiAyadi, Crystal structure and optical study of praseodymium polyphosphate Pr(PO3)3, Mater. Res. Bull. 38 (2003) 16131622.
[2] K. Horchani-Naifer, M. Frid, Crystal structure, energy band and optical
characterizations of praseodymium monophosphate PrPO4, Inorg. Chim.
Acta 362 (2009) 17931796.
[3] G. Chadeyron-Bertrand, S. Vial, J. Cellier, D. Boyer, R. Mahiou,
Inuence of processing parameters on the luminescence of solgel
derived PrPO4, Mater. Res. Bull. 40 (2005) 14771482.
[4] A. Lukowiak, A. Chiappini, A. Chiasera, D. Ristic, I. Vasilchenko,
C. Armellini, A. Carpentiero, S. Varas, G. Speranza, S. Taccheo, S. Pelli,
I.K. Battisha, G.C. Righini, W. Strek, M. Ferrari, Solgel-derived
photonic structures handling erbium ions luminescence, Opt. Quant.
Electron. 47 (2015) 117124.
[5] A. Lukowiak, R.J. Wiglusz, A. Chiappini, C. Armellini, I.K. Battisha,
G.C. Righini, M. Ferrari, Structural and spectroscopic properties of
Eu3 -activated nanocrystalline tetraphosphates loaded in silica-hafnia
thin lm, J. Non-Cryst. Solids 401 (2014) 3235.
[6] I. Vasilchenko, A. Carpentiero, A. Chiappini, A. Chiasera, A. Vaccari,
A. Lukowiak, G.C. Righini, V. Vereshagin, M. Ferrari, Inuence of
phosphorous precursors on spectroscopic properties of Er3 -activated
SiO2HfO2P2O5 planar waveguides, J. Phys.: Conf. Ser. 566 (2014)
012018.
[7] D. Palma-Ramrez, M.A. Domnguez-Crespo, A.M. Torres-Huerta,
H. Dorantes-Rosales, E. Ramrez-Meneses, E. Rodrguez, Microwaveassisted hydrothermal synthesis of CePO4 nanostructures: correlation
between the structural and optical properties, J. Alloy. Compd. 643
(2014) 209218.
[8] L. Macalik, P.E. Tomaszewski, A. Matraszek, I. Szczygiel, P. Solarz,
P. Godlewska, M. Sobczyk, J. Hanuza, Optical and structural characterisation of pure and Pr3 doped LaPO4 and CePO4 nanocrystals, J. Alloy.
Compd. 509 (2011) 74587465.

788

D. Palma-Ramrez et al. / Ceramics International 42 (2016) 774788

[9] D. Bregiroux, F. Audubert, T. Charpentier, D. Sakellariou, D. BernacheAssollant, Solid-state synthesis of monazite-type compounds LnPO4
(LnLa to Gd), Solid State Sci. 9 (2007) 432439.
[10] L. Qian, W. Du, Q. Gong, X. Qian, Controlled synthesis of light rare
earth phosphate nanowires via a simple solution route, Mater. Chem.
Phys. 114 (2009) 479484.
[11] Y.-P. Fang, A.-W. Xu, R.-Q. Song, H.-X. Zhang, L.-P. You, J.C. Yu,
H.-Q. Liu, Systematic synthesis and characterization of single-crystal
lanthanide orthophosphate nanowires, J. Am. Chem. Soc. 125 (2003)
1602516034.
[12] S. Caddick, R. Fitzmaurice, Microwave enhanced synthesis, Tetrahedron
65 (2009) 33253355.
[13] A. Kajbafvala, M.R. Shayegh, M. Mazloumi, S. Zanganeh, A. Lak,
M.S. Mohajerani, S.K. Sadrnezhaad, Nanostructure sword-like ZnO
wires: rapid synthesis and characterization through a microwave-assisted
route, J. Alloy. Compd. 469 (2009) 293297.
[14] J.F. de Lima, O.A. Serra, Cerium phosphate nanoparticles with low
photocatalytic activity for UV light absorption application in photoprotection, Dyes Pigments 97 (2013) 291296.
[15] Y. Zhang, H. Guan, Hydrothermal synthesis and characterization of
hexagonal and monoclinic CePO4 single-crystal nanowires, J. Cryst.
Growth 256 (2003) 156161.
[16] N. Clavier, R. Podor, N. Dacheux, Crystal chemistry of the monazite
structure, J. Eur. Ceram. Soc. 31 (2011) 941976.
[17] A. Monshi, M.R. Foroughi, M.R. Monshi, Modied Scherrer equation to
estimate more accurately nano-crystallite size using XRD, World J. Nano
Sci. Eng. 2 (2012) 154160.
[18] C. Yu, M. Yu, C. Li, X. Liu, J. Yang, P. Yang, J. Lin, , Facile
sonochemical synthesis and photoluminescent properties of lanthanide
orthophosphate nanoparticles, J. Solid State Chem. 182 (2009) 339347.
[19] G. Phaomei, W. Rameshwor Singh, R.S. Ningthoujam, Solvent effect in
monoclinic to hexagonal phase transformation in LaPO4:RE (RE Dy3 ,
Sm3 ) nanoparticles: photoluminescence study, J. Lumin. 131 (2011)
11641171.
[20] M.E. Poloznikova, V.V. Fomichev, The vibrational spectra and characteristic features of the orthophosphates of Group IIII elements, Russ.
Chem. Rev. 63 (1994) 399.

[21] R. Kijkowska, E. Cholewka, B. Duszak, X-ray diffraction and IRabsorption characteristics of lanthanide orthophosphates obtained by
crystallisation from phosphoric acid solution, J. Mater. Sci. 38 (2003)
223228.
[22] P. Pusztai, T. Simon, . Kukovecz, Z. Knya, Structural stability test of
hexagonal CePO4 nanowires synthesized at ambient temperature, J. Mol.
Struct. 1044 (2013) 9498.
[23] G.M.M. Sadeghi, M. Sayaf, S. Thomas, R. Shanks, S. Chandrasekharakurup,
Chapter 7-Nanostructure Formation in Block Copolymers, Nanostructured
Polymer Blends, William Andrew Publishing, Oxford, 2014, p. 195271.
[24] J. Liu, X. Ye, H. Wang, M. Zhu, B. Wang, H. Yan, The inuence of pH
and temperature on the morphology of hydroxyapatite synthesized by
hydrothermal method, Ceram. Int. 29 (2003) 629633.
[25] X. Li, J. Ma, Controlled synthesis and luminescence properties of LaPO4:
Eu phosphors, J. Lumin. 131 (2011) 13551360.
[26] K. Shinde, S.J. Dhoble, H.C. Swart, K. Park, Synthesis of Phosphate
Phosphors, Phosphate Phosphors for Solid-State Lighting, Springer,
Berlin Heidelberg, 2012, p. 6177.
[27] D. Li, R. Shi, C. Pan, Y. Zhu, H. Zhao, Inuence of ZnWO4 nanorod
aspect ratio on the photocatalytic activity, CrystEngComm 13 (2011)
46954700.
[28] S.H. Yu, B. Liu, M.S. Mo, J.H. Huang, X.M. Liu, Y.T. Qian, General
synthesis of single-crystal tungstate nanorods/nanowires: a facile, lowtemperature solution approach, Adv. Funct. Mater. 13 (2003) 639647.
[29] Y. Zhang, H. Guan, The growth of lanthanum phosphate (rhabdophane)
nanobers via the hydrothermal method, Mater. Res. Bull. 40 (2005)
15361543.
[30] V. Sivakumar, U.V. Varadaraju, Environmentally benign novel green
pigments: Pr1-xCaxPO4 (x 0-0.4), Bull. Mater. Sci. 28 (2005) 299301.
[31] A.S. Gouveia-Neto, N.P.S.M. Rios, L.A. Bueno, Spectroscopic study and
white-light simulation using praseodymium-doped uorogermanate glass
as single phosphor for white LEDs, Opt. Mater. 35 (2012) 126129.
[32] A. Saadat-Monfared, M. Mohseni, M.H. Tabatabaei, Polyurethane nanocomposite lms containing nano-cerium oxide as UV absorber. Part 1. Static
and dynamic light scattering, small angle neutron scattering and optical
studies, Coll. Surf. A: Physicochem. Eng. Aspects 408 (2012) 6470.