Available online at www.sciencedirect.

com

CERAMICS
INTERNATIONAL
Ceramics International 42 (2016) 774–788
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-Ramíreza, M.A. Domínguez-Crespoa,n, A.M. Torres-Huertaa, E. Ramírez-Menesesb,
E. Rodrígueza, H. Dorantes-Rosalesc, N. Cayetano-Castrod
a
CICATA-Unidad Altamira, Instituto Politécnico Nacional, IPN, Km 14.5, Carretera Tampico-Puerto Industrial Altamira, C. P. 89600 Altamira, Tamps., México
b
Universidad Iberoamericana, Departamento de Ingeniería y Ciencias Químicas, Prolongación Paseo de la Reforma 880, Lomas de Santa Fe C. P. 01219,
México D.F, Mexico
c
Instituto Politécnico Nacional, ESIQIE, Departamento de Metalurgia, C. P. 07300 Mexico, D.F, México
d
Instituto Politécnico Nacional, Centro de Nanociencias Micro y Nanotecnologías, Departamento de DRX, C. P. 07300 Mexico, D.F, México

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 Reflectance Diffuse Spectroscopy (DRS) and High Resolution
Transmission Electron Microscopy (HRTEM). A first 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 significant 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 including spheres, rings and other geometries exploited in

Rare-earth phosphates have ideal characteristics to be used
in fluorescent lighting, fluorescent 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 diagnos-
tic, energy conversion, telecommunications and bulk glasses
n
Corresponding author.
E-mail address: mdominguezc@ipn.mx (M.A. Domínguez-Crespo).
optical resonators fabrication [3–6]. 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 specific morphology [8]. A lot of effort has gone into
synthesizing monazite (monoclinic structure) and rhabdophane
(hexagonal phase) rare-earth phosphates under different para-
meters and methods (e. g, hydrothermal, sol–gel, wet-chemical
and high-temperature-solid–solid reaction methods) [3,9,10];
however, these methods have noticeable disadvantages. Firstly,

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.
 D. Palma-Ramírez et al. / Ceramics International 42 (2016) 774–788 775

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 morphol-
ogies and structures through a microwave-assisted-hydrother-
mal approach. The evolution from nanorod-like to spherical-
like 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 sol–gel.
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) pre-
viously prepared from the ion exchange of sodium tripolypho-
sphate Na5P3O10  5H2O (pure p.a., Z98.0% (T), Sigma-Aldrich)
using a cation exchange resin (Dowex 50 W X4 100–200 mesh),
then deionized water was added to adjust a final volume of
100 mL. The pH of the final 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 fiber optic temperature
sensor.
An initial set of experiments (see Table 1) was prepared to
assess the optimal conditions by varying the reaction tempera-
ture, synthesis time and sintering temperature (Tr, t, and Ts,
respectively). Once the initial set of experiments was com-
pleted, 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

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 þ has similar ionic
radius and 4f shell configuration as Pr3 þ , so the same behavior
would be expected in the synthesis of PrPO4. The hydrothermal
PrPO4 powders were evaluated by X-ray powder diffraction
(XRD) using a Bruker D8 Advance diffractometer equipped
with Lynxeye detector and Cu Kα radiation (λ¼ 1.5405 Å) at
35 kV and 25 mA. The data were recorded at room temperature
in the 2θ range of 15–701, step size of 0.0161 and step time
of 0.5 s.

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

Experiment pH Reaction temperature (Tr, 1C) Synthesis time (t, min) Sintering temperature (Ts, 1C) Phase composition (wt%)

Monazite Rhabdobphane

1 2 130 15 400 19.95 80.05

2 180 15 400 58.74 41.26
3 130 30 400 47.69 52.31
4 180 30 400 69.64 30.36
5 130 15 600 100 0.0
6 180 15 600 100 0.0
7 130 30 600 92.92 7.08
8 180 30 600 100 0.0
4 1 180 30 400 94.68 5.32
4 3 60.26 39.74
4 5 73.8 26.2
4 9 82.75 17.25
4 11 86.45 13.55
8 1 600 100 0.0
8 3 98.15 1.85
8 5 100 0.0
8 9 99.75 0.25
8 11 100 0.0
776 D. Palma-Ramírez et al. / Ceramics International 42 (2016) 774–788

Morphology and texture of nanopowders were examined by

high resolution scanning electron microscopy (HRSEM/EDS) T t
r130°C 15min
using a JEOL JSM-6701F equipment. Transmission electron
microscopy (TEM) micrographs were obtained with a JEM-
ARM200CF, JEOL, (Lattice resolution 78 picometers, accel- Monoclinic T r130°C t 30min

Intensity (a. u.)

eration voltage 200 kV).
FT-IR (Fourier Transform Infrared Spectroscopy) spectra Hexagonal
T r180°C t15min
were recorded on a spectrum one Perkin Elmer spectrometer
(4 cm  1 of resolution setting) in order to evaluate the

(211)
(102)
(200)
Tr t
vibrational properties of the PrPO4 bands. Samples were 180°C 30min

(301)

(302)
(103)
(300)

(203)
(103)

(140)
scanned at least 40 times in the range of 1500–450 cm  1 by

(101)

(241)
(020)

(003)
(112)
(202)
using KBr pellets.
Particle sizes were measured in a Malver Zetasizer Nano
20 30 40 50 60 70
ZSP, model ZEN5600 equipped with an Argon laser (λ¼ 633
nm) at room temperature. Previously, PrPO4 powders were 2θ (degrees)
diluted with water in a 1/100 ratio. Data were calculated from
the particle diameter moments (number-average diameter Dn;
T r180°C t30min T s600°C
weight-average diameter Dw and z-average diameter Dz), using
Eqs. (1)–(4) and the polydispersity index (PDI) was also T r130°C t30min T s600°C
determined as follows: Monoclinic T r180°C t15min T s600°C
ΣniDi T r130°C t15min T s600°C

(120)
(012)
(200)
Dn =

(311)

(132)
(322)
(103)
(1 )

(023)

(140)
(231)
(031)

(212)
(112)
Σni (101)
(110)
(111)

(111)

(202)

(241)
(114)
(014)
Intensity (a. u.)

ΣniDi 4 T r180°C t30min T s400°C

Dw = T r130°C t30min T s400°C
ΣniDi 3 (2 )
Hexagonal T r180°C t15min T s400°C
6 T r130°C t15min T s400°C
ΣniDi
(102)
(200)

Dz =

(203)
(302)
(211)
(003)

(301)

(003)
(101)

ΣniDi 5 (3 ) (112)

Dw 20 30 40 50 60 70
PDI =
Dn (4 ) 2θ (Degrees)

where ni is the number of CePO4 nanoparticles with
diameter Di.
Diffuse reflectance of the samples was evaluated by Ultra-
violet–visible diffuse reflectance spectroscopy (UV–vis DR)
using a 110-mm-diameter-integrating sphere accessory
mounted on a Cary 5000 Spectrophotometer.
The fluorescence 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 investi-
gated by the X-ray diffraction technique. The XRD patterns of
PrPO4 samples before and after being thermally treated at 400
and 600 1C (pH ¼ 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 ¼ b ¼ 7.0 Å, c ¼ 6.43
Å, ICDD 00-020-0966) and praseodymium phosphate known
as monazite (PrPO4, a ¼ 6.434 Å, b ¼ 6.760 Å, c¼ 6.982 Å,
ICDD 01-083-0653). In general, non-significant changes in the
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 þ , Ln3 þ and
Pr3 þ ) 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-hydrother-
mal 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-Ramírez et al. / Ceramics International 42 (2016) 774–788 777

Thus, to obtain a high percentage of the monoclinic Table 2

structure, the samples were thermally treated from 400 to Crystal size of PrPO4 and treatment of linear plots to obtain the crystallite size
800 1C. During the XRD measurements, however, non-impor- from Scherrer modified equation.

tant changes were observed with the sintering temperatures up Experiment pH As-prepared L (nm) Sintered L (nm)
to 600 1C. The as-treated samples at 400 and 600 1C and the eln
Kλ / L
=
0.94x 0.154051
eln
Kλ / L
=
0.94x 0.154051
L L
XRD patterns are shown in Fig. 1b. The XRD patterns of the
samples sintered at 400 1C are mainly composed of the 1 2 0.01372 11 0.0148 10
monoclinic phase (58.74 and 69.64 wt%) when a reaction 2 0.01235 12 0.0116 12
temperature of 180 1C is applied during the synthesis. As the 3 0.0116 12 0.0110 13
4 0.0122 12 0.0123 12
sintering temperature is increased from 400 to 6001 C, several
5 0.01372 11 0.0003 11
peaks of the hexagonal phase tend to shift to lower 2θ angles, 6 0.01235 12 0.0012 12
indicating the transformation to the monoclinic phase (ICDD 7 0.0116 12 0.0007 12
01-083-0653), Table 1. 8 0.0122 12 0.0004 12
A quantitative estimation of the domain size for PrPO4 4 1 0.0074 18 0.0218 7
4 3 0.0118 12 0.0119 11
nanopowders was evaluated from the three most intense peaks
4 5 0.0103 13 0.0115 12
using the Scherrer modified equation developed by A. Monshi 4 9 0.0028 48 0.0628 3
et al. [17]. The method assumes that there are N peaks of 4 11 0.0035 39 0.0410 3
specific nanocrystals which must present identical L values in 8 1 0.0074 18 0.0511 3
the range of 0–1801 (2θ) or 0–901 (θ), assumption that is not 8 3 0.0118 12 0.0096 12
8 5 0.0103 13 0.0187 12
necessarily true and consequently, the mathematically errors in
8 9 0.0028 48 0.0108 13
the calculation must be decreased by using the least squares 8 11 0.0035 39 0.0060 23
method to obtain the following equations:
Kλ Kλ 1 (Fig. 2b). Another relevant characteristic observed in this work
β= =
L. cosθ L cosθ (5 ) is that by increasing the sintering temperature from 400 to
600 1C, the signal at 956 cm  1 becomes sharper as the
Kλ Kλ 1 temperature is increased and it is related to the vibration of
In β = In = In + In
L. cosθ L cosθ (6 ) the P–O bond in the monoclinic structure [22].
The particle size distribution graphs, the average particle
After applying the least squares method, the slope calculated size (Dz), and polydispersity index (PDI) of the PrPO4 powders
from the Inβ vs In(1/ cosθ ) plot and a In(Kλ / L ) intercept can are shown in Fig. 3 and Table 3. The results in Table 3 show
be obtained using the following expression [17]. that the mean average sizes (Dz) from DLS measurements for
Kλ Kλ the as-obtained PrPO4 nanostructures range from 324 to
eIn L = 867 nm. However, the expected PDI was found to be above
L (7 )
1.5, suggesting that the PrPO4 nanoparticles are mostly
For the calculations, a K value of 0.94 was considered since composed of multiple particle populations, i.e., poly-dispersed
the shape morphology of the obtained PrPO4 has been reported systems of particles [23].
as rods [18] and the corresponding data are shown in Table 2. The morphology of the as-prepared samples is shown in
The crystallite size seems to be very stable in the 1st set of Fig. 4. It is noticeable that agglomerates of rod-like and semi-
experiments even before the sintering process (10–13 nm). spherical particles were formed independently of the synthesis
Under these conditions, the sintering temperature has not great conditions. The nanorod morphology has been reported to be
influence on the crystallite size. obtained during the synthesis of PrPO4 [11]. These nanorods
The molecular vibration of the as-prepared PrPO4 nano- tend to stack and agglomerate to each other forming larger
powders was investigated using Fourier Transform Infrared particles. It was not possible to measure with accuracy the
(FT-IR) Spectroscopy, Fig. 2a and b. The spectra displayed the length and diameter of the rods; however, a preliminary
characteristic bands c.a. 956 cm  1 and 618 cm  1, 567 cm  1 estimation of the length and diameter is about  200 nm and
and 541 cm  1 which correspond to the bending ( v4 ) and  25 nm, respectively.
stretching ( v3) vibrations of PO3− 4 , respectively [19–21],
Results of different syntheses have shown that pH is a
however, the intensity of the bands and additional bands significant parameter in altering morphology [24]. During the
emerging in the analysis highlight that the synthesis time first set of experiments, the synthesis pH was maintained
exerts a great influence on the formation of bonds. For constant to evaluate morphology changes. For this reason and
example, the sample synthesized at 180 1C and 15 min is in order to obtain more information on the pH effect on the
similar to those obtained at 130 1C (with 15 or 30 min), morphology and properties, two conditions were selected to
whereas if the time is increased to 30 min at the same synthesis evaluate the dependency on the acid or alkaline initial solution
temperature, a new vibrational band appears at 578 cm  1. This as well as the sintering temperature. Previously, it has been
band is probably related to the structural re-arrangement of found for CePO4 that by pH modulating, it is possible to obtain
PrPO4 since it is found in all the samples sintered at 600 1C a monoclinic structure at low sintering temperatures. Thus, the
778 D. Palma-Ramírez et al. / Ceramics International 42 (2016) 774–788

100 100

Transmittance (%)

Transmittance (%)
80 80

60 60

40 40

20 20

0 0
1400 1200 1000 800 600 1400 1200 1000 800 600

100 100
Transmittance (%)

80 80

60 60

40 40

20 20

0 0
1400 1200 1000 800 600 1400 1200 1000 800 600

100 100
Transmittance (%)

Transmittance (%)

80 80

60 60

40 40

20 20

0 0
1400 1200 1000 800 600 1400 1200 1000 800 600

100 100
Transmittance (%)

Transmittance (%)

80 80

60 60

40 40

20 20

0 0
1400 1200 1000 800 600 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 first set of experiments.

conditions of experiments 4 and 8, constant reaction tempera-
ture (Tr ¼ 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 vibra-
tions 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 defined 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. 6a–c. The analyzes of the XRD
 D. Palma-Ramírez et al. / Ceramics International 42 (2016) 774–788 779

25
Tr180t15Ts400 25 Tr180t15Ts400
20
Dz = 648 20 Dz = 867
PDI = 1.6 PDI = 4.2

Frequency

Frequency
15
15

10 10

5 5

0 0
0 200 400 600 800 1000 0 200 400 600 800 1000
Diameter (nm) Diameter (nm)

35 35
Tr130t30Ts400 Tr180t30Ts400
30 30
25 Dz = 324 Dz = 851
25
PDI = 3.8 PDI = 2.5
Frequency

Frequency
20 20
15 15
10 10
5 5
0 0
0 100 200 300 400 500 600 0 200 400 600 800 1000
Diameter (nm) Diameter (nm)
35
40
Tr130t15Ts600 Tr180t15Ts600
30
Dz = 377 25 Dz = 462
30 PDI = 4.4 PDI = 3.5
Frequency

Frequency

20
20 15
10
10
5
0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600 700 800
Diameter (nm) Diameter (nm)

30
Tr130t30Ts600 30 Tr180t30Ts600
25
Dz = 617 25 Dz = 433
20 PDI = 3.7 PDI = 4.0
Frequency

20
Frequency

15
15
10
10
5 5

0 0
0 200 400 600 800 1000 0 100 200 300 400 500 600 700
Diameter (nm) 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 final structure. It is easy to perceive
that by using pH ¼ 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 ¼ 3–5) and monoclinic/hexagonal structures
with small reflections emerging from the tetragonal phase at
pH ¼ 9–11 (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 reflections 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 influence on the PrPO4 crystal size was also
calculated through the Scherrer modified equation. During
the second stage of experiments (4 and 8), the crystallite size
780 D. Palma-Ramírez et al. / Ceramics International 42 (2016) 774–788

tended to increase with pH from 12 to 48 nm, but it got
reduced in the 3–23 nm interval with the sintering process
(Table 2). The pH influence can be divided into three aspects:
(i) the crystal size in acid medium (pH ¼ 1) displays a decrease
after 400 1C, (ii) at intermediate acid character (pH ¼ 3–5) the
size is almost stable and it is similar to one obtained in the first
set of experiments at pH ¼ 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)
1 648
2 867
3 324
4 pH¼1 (885)
pH¼2 (851)
pH¼3 (724)
pH¼5 (417)
pH¼9 (756)
pH¼11 (528)
5 377
6 462
7 617
8 pH¼1 (338)
pH¼2 (433)
pH¼3 (273)
pH¼5 (287)
pH¼9 (615)
pH¼11 (799)
has been reported during the synthesis of LaPO4 nanopowders
[25]. It is well known that the microwave-assisted-hydrother-
mal method reduces the activation energy of the materials, thus
lowering the synthesis temperatures of the materials, as
compared with the conventional ceramic method [26]. There-
fore, 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
PDI (Tr180t30Ts600) at different pH values are presented in
1.6 Figs. 7 and 8, respectively.
4.2 The HRTEM images proved that the nanoparticles are
3.8 composed of two types of morphologies: rods and spherical
pH¼1 (1.0) nanoparticles, which are quite dependent of the pH in the
pH¼2 (2.5)
pH¼3 (1.3)
reaction medium. As expected, the final products synthesized
pH¼5 (2.4) at pH 1 consist mainly of long rods whose length is affected by
pH¼9 (4.4) the sintering temperature; powders thermally treated at 400 1C
pH¼11 (2.0) showed diameters (D) between 12 and 30 nm with lengths (L)
4.4 ranging from 100 to 350 nm, whereas at 600 1C, shorter
3.5
nanorods were obtained (D ¼ 10–26 nm, L ¼ 40–200 nm). It
3.7
pH¼1 (1.8) is also clearly seen that by increasing the pH at 3, the nanorods
pH¼2 (4.0) start evolving to shorter and narrower sizes with lengths c.a.
pH¼3 (1.5) 20–173 nm (sintered at 400 1C) and up to 15–47 nm (sintered
pH¼5 (1.3) at 600 1C). Upon rising to pH 5, the length appearance is more
pH¼9 (1.2)
evident since the analysis of the micrographs showed particle
pH¼11 (1.1)
sizes between 7 and 50 nm, independently of the sintering

Tr130,t15,Ts400 Tr180,t15,Ts400 Tr130,t30,Ts400 Tr180,t30,Ts400

100 nm 100 nm 100 nm 100 nm

Tr130,t15,Ts600 Tr180,t15,Ts600 Tr130,t30,Ts600 Tr180,t30,Ts600

100 nm 100 nm 100 nm 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-Ramírez et al. / Ceramics International 42 (2016) 774–788 781

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 deter-
mined 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 Å, 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 T
r180 30 s400
pH 1
pH 3
Transmittance (%)
at pH 5. Different crystals belonging to the monoclinic system
at (100) (d ¼ 3.9 Å) plane are also seen. Planes (111
¯ ), (002) and
(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 tempera-
ture. The PDI values for the Tr180t30Ts400 samples show
monodisperse particles in acid medium (pH ¼ 1–3), however,
the sintering temperature modifies the particle size distribution
as it is shown by the samples prepared at Tr180t30Ts600. In the
580 566 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
542 size distribution graphs in Figs. 9 and 10. In agreement with

996 957
pH 5 615 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 9 (pH ¼ 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
pH 11 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
1400 1200 1000 800 600
-1
energy and provoke energetic rotational movements as a
Wavelength (cm ) consequence of the polarization of ions [13], providing a
platform to reduce the synthesis time and control the nuclea-
T t T
tion and growth of PrPO4 nanostructures. It has been stated
r180 30 s600 that some rare earth ions like La3 þ and PO3− 4 are stacked
pH 1 580 alternately along the [001] direction in the hexagonal crystal
566
structure of LaPO4; thus, it is reasonable to expect the
pH 3 957 praseodymium ion to be of similar ionic radii and the charge
must display a comparable behavior at low pH. It is believed
Transmittance (%)

614 539
pH 5 that the highest H þ 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
pH 9 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
pH 11 to the well-known Thomson–Gibb 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
1400 1200 1000 800 600 axis from a thermodynamic perspective, which implies that the
-1
Wavelength (cm ) growth rate along the c axis is higher than that perpendicular to
Fig. 5. FT-IR spectra of the PrPO4 nanopowders: (a) samples synthesized
the c axis. All these affecting factors drive 1D nanorods to
under experiment 4 conditions at different pH values and (b) samples grow preferentially along the [100] direction. Consequently,
synthesized under experiment 8 conditions at different pH values. the promotion of the anisotropic growth of the as-prepared
782 D. Palma-Ramírez et al. / Ceramics International 42 (2016) 774–788

T t T
*Tetragonal r180°C 30min s400° pH11

(120)
Tr180°Ct30min pH
11
* *
T t T
Tr180°Ct30min pH

(103)
(112) r180°C 30min s400° pH9
(200)

(120)
9
Monoclinic

(311)

(024)
(311)
* *

In te n s ity (a .u .)
T t T t T
Intensity (a.u.)

r180°C 30min pH5 r180°C 30min s400° pH5

(033)
(200)
(102)

Hexagonal T t
r180°C 30min pH3
Hexagonal

(1 0 2 )
(320)
(211)
(112)
(101)

T t T
(301)

(203)
(302)

(1 0 3 )
(323)
r180°C 30min s400° pH3

(1 1 2 )
(0 2 0 )
(1 0 1 )

(3 2 2 )
Monoclinic T t
(012)

r180°C 30min pH1

(120)

T t T

(0 0 2 )
(322)
(132)
(023)

(014)
(014)
(140)
(004)
(103)

r180°C 30min s400° pH1

(0 1 2 )
(112)
(031)
(202)

(231)
(200)

(212)
(103)

(340)
(020)
(111)
(011)

(3 0 1 )
(3 1 1 )

(1 0 3 )

(4 0 0 )
(1 3 2 )
20 30 40 50 60 70 20 30 40 50 60 70

2 θ (degrees) 2 θ (Degrees)

Tr180°Ct30minTs600° pH
11

T t T
(002)
(002)

r180°C 30min s600° pH9

(431)
(120)

T t T
Intensity (a.u.)

r180°C 30min s600° pH5

(111)

T t T
r180°C 30min s600° pH3

Monoclinic T t T
(122)

r180°C 30min s600° pH1

(012)
(002)

(004)
(103)
(212)

(014)
(140)

(124)
(322)
(132)
(103)
(231)
(023)
(202)
(112)
(031)
(111)
(020)
(200)
(110)

20 30 40 50 60 70
2 θ (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 presence of a small amount of free PO3− 4 ions, where the motion
effect including the intrinsic structural features of specific speed reached a maximum value [29].
faces, local solution details, foreign energy activation and During the synthesis of PrPO4, nucleuses of tiny crystals are
autogenous pressure [28]. formed and subsequently the crystal grows generating the
On the other hand, when increasing the pH value, a semisphe- semispherical particles. There are higher OH  ion concentra-
rical-type morphology is favored. According to previous works tions which are absorbed onto the crystal facets, producing a
related to rare earth phosphates, colloidal precipitates have been double layer composed of cations (H þ and NH4þ ) and anions
observed as the pH value of the solution was decreased [29]. (NO-3 and OH  ) as shown in Fig. 11.
However, in this work, precipitates were more evident in alkaline By taking into account these facts and considering those
than in acid medium. The precipitates were associated with the already established in the literature [15,29], the most probable
 D. Palma-Ramírez et al. / Ceramics International 42 (2016) 774–788 783

reactions of the PrPO4 formation, either in acid or alkaline Pr(NO3)3 (aq)⋅6H 2O + HNO3 (aq) + H 3PO4(aq)
solutions, can be proposed as follows:
Reaction in acid medium: → PrPO4(s) ↓ + 4HNO3(aq) + nH 2O(aq) (10)

H 5P3O10(aq) + H 2O (aq) → H4P2O7(aq) + H 3PO4(aq) (8 ) Reaction in alkaline medium:

H4P2O7 + H 2O → 2H 3PO4 (9 ) 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-Ramírez et al. / Ceramics International 42 (2016) 774–788

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 reflectance 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 4f–4d transitions
of the following energy levels: 3H4-3P2, 3H4-3P1,
3
H4-3P0, 3H4-3D2 (upper) and 3H4-3D2 (lower), respec-
tively [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-Ramírez et al. / Ceramics International 42 (2016) 774–788
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 Kubelka–Munk 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 final application,
the fluorescence 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 modified in acid
conditions with that obtained in alkaline media afforded the
high association of the pH with the morphological properties
and the final photonic properties of PrPO4nanostructures.
Comparing the two emission spectra, it can be found that
PrPO4 nanorods (i.e. sample obtained at pH ¼ 1) spectrum
consists mainly of two separated bands of fluorescence with
maxima at  510 nm and  610 nm which are due to the
3
P0-3H5 and 1D2-3H4 transitions of Pr3 þ in the sample
[31]. Results reveal no significant dependence of emission on
785
the sintering temperature. In the case of smaller particles
(obtained at pH ¼ 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 ¼ 9.
Typically semi-conductor material used as UV absorber
works by absorbing photons producing electron–hole 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 pre-
pared by the microwave-assisted-hydrothermal method from Pr
786 D. Palma-Ramírez et al. / Ceramics International 42 (2016) 774–788

20 25

20
15

Frequency
Frequency
15
10
10

5 5

0 0
0 100 200 300 400 500
Diameter (nm)

30
25
25
20
20

Frequency
Frequency

15
15

10 10

5 5

0 0
0 100 200 300 400 500 600 0 200 400 600 800 1000
Diameter (nm) Diameter (nm)

25

20
Frequency

15

10

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 materials. The study also demonstrates that by using this
method was simple and easily repeated and could be devel- method and modulating the pH, the hexagonal structure is
oped for the synthesis of different rare earth phosphate transformed into the monoclinic one. Even this transformation
 D. Palma-Ramírez et al. / Ceramics International 42 (2016) 774–788 787

4 (Tr180°Ct30minTs400°C)
Tr t Ts
Tr180°Ct15minTs600°C 180°C 30min 400°C 8 (Tr180°Ct30minTs600°C)
Tr130°Ct30minTs400°C 8 (pH 3)
100
100 Tr130°Ct15minTs600°C
8 (pH 1)

4 (pH 5)
D iffuse reflectance (% )

80

Diffuse reflectance (%)

80 4 (pH 3)

60
60 4 (pH 1)

Tr130°Ct15minTs400°C Tr180°Ct30minTs600°C 8 (pH 5)

40
Tr180°Ct30min
40
Tr130°Ct30min Tr130°Ct30minTs600°C
8 (pH 9) 8 (pH 11)
20 4 (pH 11)
Tr180°Ct15minTs400°C
20 Tr130°Ct15min

Tr180°Ct15min 0
4 (pH 9)
0
200 300 400 500 600 700 200 300 400 500 600 700
λ (nm) λ (nm)
Fig. 12. Diffuse reflectance 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
are also grateful for the financial support provided by CON-
Tr180°Ct30minTs600°C pH 1 ACYT through the CB2009-132660 and CB2009-133618
140 projects and to IPN through the SIP 2015-0202 and 2015-
Tr180°Ct30minTs600°C pH 9
510 nm 0227 projects and SNI-CONACYT.
120
Tr180°Ct30minTs400°C pH 1
Emission Intensity

100
80
60
40
20
0 derived PrPO4, Mater. Res. Bull. 40 (2005) 1477–1482.
450
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, co-
precipitation, solvothermal or sol–gel 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-Ramírez is grateful for her postgraduate scholar-
ship to CONACYT, SIP-IPN and COFAA-IPN. The authors
References
610 nm [1] A. Jouini, M. Ferid, J.-C. Gâcon, L. Grosvalet, A. Thozet, M. Trabelsi-
Ayadi, Crystal structure and optical study of praseodymium polypho-
sphate Pr(PO3)3, Mater. Res. Bull. 38 (2003) 1613–1622.
[2] K. Horchani-Naifer, M. Férid, Crystal structure, energy band and optical
characterizations of praseodymium monophosphate PrPO4, Inorg. Chim.
Acta 362 (2009) 1793–1796.
[3] G. Chadeyron-Bertrand, S. Vial, J. Cellier, D. Boyer, R. Mahiou,
Influence of processing parameters on the luminescence of sol–gel
500 550 600 650 [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, Sol–gel-derived
photonic structures handling erbium ions luminescence, Opt. Quant.
Electron. 47 (2015) 117–124.
[5] A. Lukowiak, R.J. Wiglusz, A. Chiappini, C. Armellini, I.K. Battisha,
G.C. Righini, M. Ferrari, Structural and spectroscopic properties of
Eu3 þ -activated nanocrystalline tetraphosphates loaded in silica-hafnia
thin film, J. Non-Cryst. Solids 401 (2014) 32–35.
[6] I. Vasilchenko, A. Carpentiero, A. Chiappini, A. Chiasera, A. Vaccari,
A. Lukowiak, G.C. Righini, V. Vereshagin, M. Ferrari, Influence of
phosphorous precursors on spectroscopic properties of Er3 þ -activated
SiO2–HfO2–P2O5 planar waveguides, J. Phys.: Conf. Ser. 566 (2014)
012018.
[7] D. Palma-Ramírez, M.A. Domínguez-Crespo, A.M. Torres-Huerta,
H. Dorantes-Rosales, E. Ramírez-Meneses, E. Rodríguez, Microwave-
assisted hydrothermal synthesis of CePO4 nanostructures: correlation
between the structural and optical properties, J. Alloy. Compd. 643
(2014) 209–218.
[8] L. Macalik, P.E. Tomaszewski, A. Matraszek, I. Szczygiel, P. Solarz,
P. Godlewska, M. Sobczyk, J. Hanuza, Optical and structural character-
isation of pure and Pr3 þ doped LaPO4 and CePO4 nanocrystals, J. Alloy.
Compd. 509 (2011) 7458–7465.
788 D. Palma-Ramírez et al. / Ceramics International 42 (2016) 774–788
[9] D. Bregiroux, F. Audubert, T. Charpentier, D. Sakellariou, D. Bernache-
Assollant, Solid-state synthesis of monazite-type compounds LnPO4
(Ln¼La to Gd), Solid State Sci. 9 (2007) 432–439.
[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) 479–484.
[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)
16025–16034.
[12] S. Caddick, R. Fitzmaurice, Microwave enhanced synthesis, Tetrahedron
65 (2009) 3325–3355.
[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) 293–297.
[14] J.F. de Lima, O.A. Serra, Cerium phosphate nanoparticles with low
photocatalytic activity for UV light absorption application in photopro-
tection, Dyes Pigments 97 (2013) 291–296.
[15] Y. Zhang, H. Guan, Hydrothermal synthesis and characterization of
hexagonal and monoclinic CePO4 single-crystal nanowires, J. Cryst.
Growth 256 (2003) 156–161.
[16] N. Clavier, R. Podor, N. Dacheux, Crystal chemistry of the monazite
structure, J. Eur. Ceram. Soc. 31 (2011) 941–976.
[17] A. Monshi, M.R. Foroughi, M.R. Monshi, Modified Scherrer equation to
estimate more accurately nano-crystallite size using XRD, World J. Nano
Sci. Eng. 2 (2012) 154–160.
[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) 339–347.
[19] G. Phaomei, W. Rameshwor Singh, R.S. Ningthoujam, Solvent effect in
monoclinic to hexagonal phase transformation in LaPO4:RE (RE ¼Dy3 þ ,
Sm3 þ ) nanoparticles: photoluminescence study, J. Lumin. 131 (2011)
1164–1171.
[20] M.E. Poloznikova, V.V. Fomichev, The vibrational spectra and char-
acteristic features of the orthophosphates of Group I–III elements, Russ.
Chem. Rev. 63 (1994) 399.
[21] R. Kijkowska, E. Cholewka, B. Duszak, X-ray diffraction and IR-
absorption characteristics of lanthanide orthophosphates obtained by
crystallisation from phosphoric acid solution, J. Mater. Sci. 38 (2003)
223–228.
[22] P. Pusztai, T. Simon, Ã. Kukovecz, Z. Kónya, Structural stability test of
hexagonal CePO4 nanowires synthesized at ambient temperature, J. Mol.
Struct. 1044 (2013) 94–98.
[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. 195–271.
[24] J. Liu, X. Ye, H. Wang, M. Zhu, B. Wang, H. Yan, The influence of pH
and temperature on the morphology of hydroxyapatite synthesized by
hydrothermal method, Ceram. Int. 29 (2003) 629–633.
[25] X. Li, J. Ma, Controlled synthesis and luminescence properties of LaPO4:
Eu phosphors, J. Lumin. 131 (2011) 1355–1360.
[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. 61–77.
[27] D. Li, R. Shi, C. Pan, Y. Zhu, H. Zhao, Influence of ZnWO4 nanorod
aspect ratio on the photocatalytic activity, CrystEngComm 13 (2011)
4695–4700.
[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, low-
temperature solution approach, Adv. Funct. Mater. 13 (2003) 639–647.
[29] Y. Zhang, H. Guan, The growth of lanthanum phosphate (rhabdophane)
nanofibers via the hydrothermal method, Mater. Res. Bull. 40 (2005)
1536–1543.
[30] V. Sivakumar, U.V. Varadaraju, Environmentally benign novel green
pigments: Pr1-xCaxPO4 (x ¼0-0.4), Bull. Mater. Sci. 28 (2005) 299–301.
[31] A.S. Gouveia-Neto, N.P.S.M. Rios, L.A. Bueno, Spectroscopic study and
white-light simulation using praseodymium-doped fluorogermanate glass
as single phosphor for white LEDs, Opt. Mater. 35 (2012) 126–129.
[32] A. Saadat-Monfared, M. Mohseni, M.H. Tabatabaei, Polyurethane nano-
composite films 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) 64–70.