Journal of Crystal Growth 426 (2015) 86–94

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Journal of Crystal Growth

journal homepage: www.elsevier.com/locate/jcrysgro

Growth, crystalline perfection, optical, thermal, laser damage threshold

and electrical characterization of melaminium levulinate monohydrate
single crystal
N. Sivakumar a, N. Kanagathara b, G. Bhagavannarayana c, S. Kalainathan d, G. Anbalagan e,n
a
Department of Physics, Saveetha School of Engineering, Saveetha University, Chennai 600077, India
b
Vel Tech Dr. RR Dr. SR Technical University, Avadi, Chennai 600062, India
c
Materials Characterization Division, National Physical Laboratory, New Delhi 110012, India
d
Department of Physics, VIT University, Vellore 632014, India
e
Department of Physics, Presidency College, Chennai 600077, India

art ic l e i nf o a b s t r a c t

Article history: Equimolar amounts of melamine and levulinic acid results an organic crystal of melaminium levulinate
Received 29 September 2014 monohydrate (MLM) at room temperature. MLM belongs to a monoclinic crystal structure having P21/c
Received in revised form space group which was confirmed by single crystal X-ray diffraction study. Functional groups present in
20 May 2015
the MLM crystal were identified by FT-IR spectral study. HRXRD study dictates the quality of MLM
Accepted 23 May 2015
Available online 2 June 2015
crystal. UV–visble spectrum of MLM reveals the lower cut-off wavelength of 293 nm with 55% optical
transparency and optical band gap was found to be 4.20 eV for the prominent plane (1 0
1). Refractive
Keywords: indices for the three axes of MLM crystal were found to be nx ¼2.6, ny ¼ 2.4 and nz ¼ 2.2 respectively.
A1. Crystal morphology Further the thermal stability and melting point of MLM crystal were investigated by TG/DTA study.
A1. High resolution X-ray diffraction
Dielectric permittivity tensor components were estimated for the planes (1 0
1), (0 1 0) and (1 1 1)
A2. Growth from solutions
respectively. The thermal conductivity of the crystal by Wiedemann—Franz law was found to be
B1. Organic compounds
B2. Dielectric materials 5.99  10–11 W/mK at 70 1C. LDT value (2.84 GW/cm2) of MLM was estimated for laser optical device
applications.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction growth and optical, dielectric characterization of melaminium bis

(trifluoroacetate) trihydrate single crystal. Combination of various
The growth of single crystals with self assembled hydrogen organic and inorganic acids with melamine forms an interesting
bonds in the molecular structure is of great interest in crystal hydrogen bond system. Because of its versatility, this melamine is
engineering [1,2]. Currently, much attention is given to hybrid taken as the subject of interest. Levulinic acid is a well known
organic–inorganic crystals because of their large hyperpolarizabil- example of a very attractive chemical from biomass. Due to the
ity and high laser damage resistance compared to inorganic presence of two reactive functional groups, i.e. a ketonic and a
materials [3,4]. Melamine, an organic base is a trimer of cynamide carboxylic group, levulinic acid is one of the most bio-based
having a skeleton of 1,3,5-triazine. The complexes of melamine are multipurpose molecules [11]. Its functionalized carbon structure
results in π–π aromatic ring stacking with self-assembled hydrogen is widely used as a chemical intermediate in the manufacture of
bonded molecular networks [5,6]. Melamine and their complexes fuel extenders, biodegradable polymers, herbicides, antibiotics and
are widely used industrial chemicals in the manufacture of dyes, flavors [12,13]. SooChoi et al. [14] reported the melaminium
plastics, fertilizers, textiles and its polymers play an important role levulinate monohydrate crystal structure with the chemical for-
in technological applications [7,8]. In polymers like epoxy resins, mula (C3H7N6þ  C5H7O3
 H2O). The results of the reported struc-
cellulose or flax fibers, melamine acts as a flame retardant agent. ture reveal the monoclinic system of MLM crystal with Z¼4 and
Due to the presence of amino groups, melamine derivatives lattice cell parameters are a¼ 10. 538 Å, b¼ 16. 214 Ǻ, c ¼7. 198 Ǻ
develop well defined self-organized super lattices through donor and space group P21/c. Co-crystal of melamine and levulinic acid
and acceptor hydrogen bonds. [9]. Sangeetha et al. [10] reported was stabilized through self-assembled hydrogen bond networks.
Four N–H…O and two N–H…N hydrogen bonds link two melami-
nium molecules in which two pairs of each N–H…O bond connect
n
Corresponding author. Tel.: þ 91 94871 40051. the two H-atoms belong to two amine groups of melamine cations
E-mail address: anbu24663@yahoo.co.in (G. Anbalagan). through O-atom of single levulinate [14].

http://dx.doi.org/10.1016/j.jcrysgro.2015.05.025
0022-0248/& 2015 Elsevier B.V. All rights reserved.
 N. Sivakumar et al. / Journal of Crystal Growth 426 (2015) 86–94 87

The present research work describes the bulk growth of good then allowed for continuous stirring for about 1 h to ensure the
quality melaminium levulinate monohydrate (MLM) using the temperature homogeneity. Fig. 2 reveals the positive solubility
solvent evaporation technique. For the first time, we are reporting gradient of MLM crystal. A trend of this solubility curve is quite
the solubility and dielectric properties with TG/DTA studies. In enough for the bulk growth of crystals by slow cooling as well as
addition to these studies, MLM crystal is subjected to optical and slow evaporation techniques. Supersaturation state is acting as a
surface laser damage threshold analysis and their details are driving force of crystallization, in which the concentration of
discussed completely. solute molecules will be more when compared to that of solubility
state at a given temperature. In the supersaturation range called
metastable zone, the spontaneous crystallization is not possible.
2. Experimental details Metastable zone width mainly depends on the presence of
impurity, cooling and stirring rates. Hence, in the growth of
2.1. Material preparation crystals, controlled crystallization can be achieved. In the present
case, we estimated the metastable zone width of MLM in the
The equimolar ratio of melamine and levulinic acid was taken binary solvent of methanol–water.
for the synthesis of melamine levulinate monohydrate (MLM). A Constant temperature water bath was utilized for the nucleation
hot aqueous solution of melamine was prepared at 45 1C and studies of MLM crystal for the temperatures 35, 40, 45, 50 and 55 1C.
levulinic acid was gently added to this solution. Homogeneous When the solution reaches supersaturation state, it is allowed to cool
solution was obtained by stirring it for about 7 h. In this reaction a slowly by a cryostat unit. At a particular lower temperature, the
proton is transferred from the electron donor group of levulinic formation of first crystal nuclei was observed and is called critical
acid to the electron acceptor group of melamine. The resultant nuclei. The difference in temperature between the states of satura-
product is melaminium levulinate monohydrate (MLM), in which tion and nucleation determines the value of metastable zonewidth
the levulinate anion and melaminium cation result from proton [16]. Fig. 2 shows the metastable zonewidth of MLM solution in
transfer. The resultant solution was kept undisturbed in a dust free which zonewidth decreases as the temperature increases. The large
atmosphere. Crystalline salt of MLM was obtained after 2 weeks of metastable zone width of the crystalline material indicates the fast
solvent evaporation. Five times of the crystallized salt were used to growth rate and stability of growth solution.
prepare the saturated solution at 30 1C. The solution was filtered in
a beaker using filter paper (Whatmann) and is allowed for
2.3. Characterization
evaporation. Rate of evaporation has been controlled by closing
the neck of the beak with polythene sheet having less number of
The grown crystal of MLM was subjected to single crystal XRD
micrometer sized holes. The beaker was then placed in a constant
analysis in order to determine the lattice parameters and morphology
temperature bath having 70.01 1C accuracy. Optically clear and
chemically stable MLM crystal with dimension of 20  20  7 mm3
was harvested after 10 days of controlled solvent evaporation at 7.0 Nucleation curve
room temperature. The photograph of as-grown crystal with well Solubility curve
defined morphology of MLM are shown in Fig. 1. 6.5
Concentration (g/100 ml)

2.2. Solubility and meta stable zone width 6.0

Solubility of the solute molecules present in the solvent will 5.5

decides the shape, growth and size of the crystals. The materials
th
id
ew

solubility depends on factors like temperature and impurity which 5.0

on
ez

defines the supersaturation and is the driving force for the

bl
ta
as

nucleation. Growth of bulk crystals is mainly influenced by the 4.5

et
M

two key factors, (i) dipole moments between crystal component

and the solvent, (ii) heat of crystallization [15]. The synthesized 4.0
salt of MLM was subjected to solubility study using an equivalent
ratio of water-methanol solvent. Solubility study was carried out 30 35 40 45 50 55
over the wide range of temperatures from 35 1C to 55 1C insteps of Temperature (°C)
5 1C using constant temperature bath with Eurotherm controller Fig. 2. The metastable zone of MLM solution in binary solvent of methanol
(of accuracy 70. 01 1C). Water bath was initially kept at 35 1C and and water.

Fig. 1. Photograph of (a) as-grown and (b) morphology of MLM crystal.

88 N. Sivakumar et al. / Journal of Crystal Growth 426 (2015) 86–94

using ENRAF NONIUS CAD4 X-ray diffractometer with MoKα (λ¼ 0. 3. Results and discussion
71073 Å) radiation. The orientation matrix and unit cell parameters
were determined using 25 reflections measured by ‘search’ routine. 3.1. X-ray diffraction and morphology studies
Once the orientation matrix is determined, the morphology (Miller
indices of all developed faces) could be measured using the standard The results of single crystal XRD confirm the monoclinic crystal
procedure mentioned in CAD4 manual. A Perkin–Elmer Spectrum One structure with centrosymmetric space group P21/c. The calcula-
Fourier transform infrared spectrometer was employed to determine ted cell parameters are a ¼11.235 Å, b¼17.435 Å, c ¼6.998 Å, β¼
the infrared spectrum at room temperature in the range of 4000– 108.8o and V¼ 1370.78 Å3. The single crystal XRD data of MLM are
450 cm
1. The sample was prepared by pressing the crystal powder very well matched with the reported values [14].
with KBr to a pellet form. A multicrystal X-ray diffraction (HRXRD) It was observed that the crystal has eight prominent morpholog-
system with MoKα1 radiation was employed to assess the crystalline ical faces, namely (
1
1
1), (0
1 0), (0
1 1), (1 1 1), (0 1 0),
perfection of the growing crystal. The UV–Visible spectral analysis was (0 1
1), (1 0
1) and (
1 0 1) with c-axis along the length of the
carried out between 200 and 800 nm using Varian Cary 5E UV–Visible crystal. The (1 0
1) plane was found to be perfectly flat and per-
Spectrophotometer. According to the crystal structure, The asymmetric pendicular to (0 1 0) plane. The unit cell has the shortest dimension
unit of consists of two oppositely charged ions, viz. a protonated along the c-axis.
melaminium ion and a levulinate ion, and one water molecule along
the b-axis. The two water molecules are involved in bridging melami- 3.2. High resolution XRD analysis
nium and levulinate entities in the next row along the b axis stacked
almost parallel to each other and to the (1 0
1) crystallographic The rocking curves of the crystals for the diffraction planes were
plane [9]. The three well developed planes (1 0
1), (0 1 0) and (1 1 1) recorded in symmetrical Bragg geometry using the natural facets by
were identified from the morphology of the crystal through the crystal performing ω scan [17] with double-axis geometry. The monochro-
structure (Fig. 1(b)). These crystal planes used for measurements were mated X-ray beam incident on the specimen was obtained using a
cut parallel to X-, Y-, and Z-axis respectively, and these planes were high-resolution four-bounce Ge(2 2 0) monochromator. A scintillation
subjected to the UV and dielectric measurements. The electrical detector was used to record the diffracted beam from the crystal
behavior of the grown crystal was tested by dielectric studies using a sample without using any analyzer at the receiving stage (i.e. before
HIOKI model 3532-50 LCR HITESTER in the frequency range of the detector) to get all the possible information like the individual
100 Hz–5 MHz at an applied voltage of 1 mV. Transparent good quality peaks from structural grain boundaries, scattered intensity from the
crystal of dimensions for (1 0
1) plane 6.75  5.56  1.77 mm3 ( for dislocations and other defects from the specimen crystal. The recorded
(0 1 0) plane 6.70  2.47  1.40 mm3 and for (1 1 1) plane 4.16  rocking curve (or diffraction curve) of MLM specimen is shown in
3.86  1.15 mm3) was polished and electronic grade silver paste was Fig. 3. A single high intensity rocking curve reveals that the grown
applied on either side of the sample, which acts as an electrode. The crystal does not have any structural grain boundaries. The FWHM
measurements were carried out on the parallel circuit mode using the value of MLM crystal for the (1 0
2) plane was found to be 46 arc
two-probe setup. The parallel capacitance Cp and dissipation factor sec. According to a plane wave dynamical theory of X-ray diffraction
(D¼ tan δ) were obtained from the measurements and all other [18], the FWHM value of MLM crystal is quite higher than that for an
parameters were calculated from these data. Dielectric measurements ideal perfect crystal which could be in the range of a fraction of an arc
of MLM along different crystallographic directions were carried out sec to a few arc sec. The broadening of HRXRD rocking curve without
with single-crystal samples. Crystal faces are selected in accordance much asymmetry with respect to peak position and without the
with its structure data. Laser damage threshold on MLM crystal was presence of any shoulder peaks can be attributed to defects like
measured by using Q-switched Nd:YAG laser at a wavelength of Frankel defects (due to the simultaneous existence of vacancies as well
1064 nm. Thermal analysis was performed with a simultaneous TG/ as interstitial defects), dislocations and mosaic blocks etc. [19]. How-
DTA instrument (SDT Q 6000 V 8.2 Built 100 thermal analyzers). The ever, crystals with a lesser defect density of these can not affect the
experimental conditions were as follows: (i) continuous heating from device performance. But the increase of defect density leads to
room temperature to 1000 1C at a heating rate of 20 1C/min, (ii) N2-gas structural grain boundaries in the crystals [20]. Growth conditions as
dynamic atmosphere (90 cm3 min
1), (iii) alumina, as reference well as thermodynamic considerations also result in point defects in
material and (iv) sample: 4.1310 mg of the sample without pressing. the crystals and are unavoidable up to some extent [21].

3.3. FT-IR spectral studies

MLM
Functional groups present in the synthesized compounds can
250000 be easily identified using Infrared spectroscopy and the recorded
MoKα
FT-IR spectrum of MLM crystal is depicted in Fig. 4. Melaminium
complexes form hydrogen bonds of N–H…O and N–H…N types.
200000
Diffracted X-ray intensity [c/s]

The O–H stretching is generally strong in IR spectrum. The strong

peak observed at 3500 cm
1 in the infrared spectrum is due to the
150000 OH stretching of water molecules. The strong and broad IR peak
observed at 3389 cm
1 is ascribed to symmetric N–H stretching
46" vibration of hydrogen bonded NH2 of melamine. The medium
100000 strong infrared band at 3191 cm
1 is attributed to N–H…O and O–
H…O stretching and the band at 2354 cm
1 indicates the N–H…O
50000
stretching vibration. There are four IR peaks at 3013, 2934, 2736
and 2690 cm
1 with medium intensity due to CH3 and CH2
stretching vibrations present in the levulinic acid [22]. The sym-
0 metric C ¼O stretching (ketone group) of levulinic acid occurs at
-150 -75 0 75 150
1715 cm
1. The very strong infrared peak at 1652 cm
1 is assigned
Glancing angle [arc sec]
to NH2 bending type of vibration [23]. The weak IR peak at 1541 is
Fig. 3. High resolution X-ray diffraction curve recorded for a typical MLM crystal. assigned to the side chain asymmetric C–N stretching vibration.
 N. Sivakumar et al. / Journal of Crystal Growth 426 (2015) 86–94 89

Table 1
Molecular vibrational assignments of MLM crystal.

FT-IR (cm
1) Assignments

3500 ms O–H stretching of water

3389 ms N–H symmetric stretching
3191 ms N–H…O and O–H…O stretching
3013 ms CH3 stretching
2934 ms CH3 stretching
2736 m CH3 stretching
2690 m CH2 stretching
2490 m NH2 bending
2354 m N–H…O stretching
1715 ms C¼ O symmetric stretching
1652 ms NH2 bending
1541 s C–N asymmetric stretching (side-chain)
1469 s C–N stretching
1403 s C–N Ring and side chain stretching
1298 ms CH2 wagging
1230 ms C–H in-plane bending
Fig. 4. FT-IR spectrum of MLM crystalline powder recorded at room temperature. 1196 ms NH2 rocking
1171 m CH2 in-plane bending
1069ms CH2 out-of plane bending
1041 m Triazine ring vibration
The very strong IR peak at 1403 cm
1 is attributed to C–N ring and the
1018 m Triazine ring vibration
side chain stretching vibrations. The medium strong IR peak at 1298 991 ms Triazine ring radial type vibration
cm
1 in the experimental spectrum is assigned to the CH2 wagging 939 ms C–C stretching
type of vibration [13]. In the case of pure levulinic acid, this peak is 910 ms O–H in-plane bending
appeared at 1280 cm
1. The difference in 18 cm
1 hereby confirmed 797 s Ring sextant out-of plane bending
723 s CH2 out-of plane bending
the formation of crystal structure. The medium strong infrared peak at 682ms Symmetric type triazine ring
1230 cm
1 is assigned to C–H in-plane bending vibration. NH2 rocking 647ms C¼ O out-of plane deformation
vibrations contribute its mode at 1196 cm
1 with medium strong 614 m Ring bending
intensity. The medium IR peak at 1069 cm
1 is assigned to CH2 out-of- 562 s COOH deformation
522 s C–O out-of plane bending
plane bending vibration. In the present case, the weak infrared peaks
at 1041 and 1018 cm
1 are assigned to triazine ring vibration. A med-
ium infrared band at 991 cm
1 is also assigned to triazine ring radial
type vibration [24]. The weak infrared peak at 939 and 910 cm
1 are
ascribed to C–C stretching and O–H in-plane bending vibration [22].
The strong infrared peak at 797 cm
1 is due to ring-sextant-out-of-
plane bending vibration [25]. In pure melamine crystal, this peak is
observed at 814 cm
1 with strong intensity. The lowering of this
wavenumber further gives the evidence for the formation of MLM
crystal. The strong infrared band at 682 cm
1 is attributed to sym-
metric type vibration of the triazine ring. The medium strong infrared
band at 647 cm
1 is assigned to C¼O out-of-plane deformation. The
ring bending vibration is appeared at 614 cm
1 with medium
intensity. The strong infrared band at 562 cm
1 is due to COOH
deformation and the strong IR peak observed at 522 cm
1 is due to
C–O out-of plane bending vibration. The other vibrational assignments
are compiled in Table 1.

3.4. Optical studies

The optical transparency of a crystal also depends on defects in Fig. 5. (a) UV–visible transmittance spectrum and (b) Tauc's plot of (αhυ)2 vs.
photon energy (hυ) of MLM crystal.
single crystal which in turn acts as light absorbing/scattering
centers [26]. Therefore, it is essential to study the optical transmi-
ttance of the grown crystals. Fig. 5(a) shows the optical transmit-
of electronic transition and band structure of the optical materials
tance spectrum of MLM single crystals. The cut-off wavelength of
can be easily understood by the optical absorption coefficient and
both the samples is found to be 293 nm. From the figure, it is
can be evaluated using the standard equation,
observed that the crystals are transparent from 293 nm to 900 nm


wavelength region. The lower cut-off wavelength with maximum 1 1
α ¼ log 10 ð1Þ
transmittance (55%) is due to π-πn transition in nitrogen- t T
containing aromatic systems which results in the blue end of the
where T is the optical transmittance and t is the crystal thickness.
spectrum [27].
Tauc's expression relates the absorption coefficient (α) and photon
energy (hυ) and given by the expression [28],
3.4.1. Band gap energy calculation
αhυ ¼ βðhυ
Eg Þ1=2 ð2Þ
The fundamental physical quantities of optical materials like
optical energy band gap and linear refractive index characterize where α is the absorption coefficient, hυ is the incident photon
the electrical and optical properties of the grown crystal. The type energy, Eg is the optical band gap energy and β is the optical
90 N. Sivakumar et al. / Journal of Crystal Growth 426 (2015) 86–94

materials constant. The plot for direct transition is shown in Fig. 5 from MLM. The corresponding DTA peak occurs at 73.34 1C. The
(b). By extending a straight line from the linear portion of the dehydration in the crystalline materials is due to dipole–ion
curve to the x-axis ((αhυ)2 ¼ 0), the optical band gap energy is interaction between the effective ionic charge and dipole moment
found to be Eg ¼4.20 eV. Thus, the good optical transparency of the of water molecules. Thermal energy in the crystal rises due to the
MLM crystal has been confirmed by the wide optical band gap increase of temperature, which results in breaking of bond
energy which ensures the crystal suitability for opto-electronic effective ionic charge and water molecules. Further increase of
device applications [29]. temperature, thermal energy of the material reaches a maximum
value and thus the water molecules present in the materials are
3.4.2. Refractive index estimation free and escapes from the crystal lattice [31]. The second decom-
The refractive index of the material can be understood by the position stage of MLM has been observed in the temperature
interaction of light with matter and is an important criterion for interval from 130.26 to 190.99 1C with a significant weight loss of
optical device fabrications. Refractive index estimation has a vital 39.03%, which is accompanied by the elimination of levulinic acid
role in optical parameter calculations as well as NLO applications anions and the corresponding DTA peak is observed at 126.21 1C.
like frequency doubling experiments. In order to find the refractive The third stage of decomposition of MLM starts at 261.72 1C and
index along three different crystallographic directions, the UV–vis continues up to 318.40 1C, with a rapid weight loss of 45.58%
spectra were recorded on the three different planes cut along the which is followed by a DTA at 314.59 1C. The weight loss at the
planes (1 0
1), (0 1 0), (1 1 1). The extinction coefficient (K) as a third stage is attributed to the removal of melaminium cations
function of wavelength (λ) can be represented by the equation, from the MLM crystal structure with 0.016 mg as its residue. An
endothermic peak of DTA at 185.04 1C indicates the melting of
λα
Κ¼ ð3Þ MLM crystal. However, the high degree of crystallinity of MLM was
4π
further confirmed by sharp endothermic peaks observed in the
Optical reflectance (R) as well as the refractive index (n) can be DTA spectrum.
estimated using the following relations,
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
expð
αtÞ 7 expð
αtÞT
expð
3αtÞT þ expð
2αtÞT 2
R¼ ð4Þ
expð
αtÞ þ expð
2αtÞT
pffiffiffi

ðRþ 1Þ 7 2 R
n¼ ð5Þ
ðR
1Þ
2.9
From the above relations, it can be understood that the absorption
coefficient determines the optical constants and is an essential tool 2.8
to improve the internal efficiency of the optical materials. Thus, by
tuning the band gap energy as well as orienting the absorption 2.7
coefficient one can get a suitable material for efficient electro-
2.6
Rrfractive index

optical devices.
Single crystal of as-grown monoclinic MLM belongs to centro-
2.5
symmetric space group P21/c which shows the center of inversion.
Optical indicatrices are dispersive for the monoclinic crystal and
2.4
their orientations and shapes are depends on incident light
wavelength. The optical properties of the crystals can be explained 2.3
by an optical ellipsoid with three perpendicular principal axes Nx,
Ny and Nz with associated refractive indices nx 4ny 4nz respec- 2.2
tively. For a monoclinic system, the principal optical axis Nz and
the b crystallographic direction coincide with each other and Nx, 2.1
Ny axes are presented in a–c crystallographic planes [10]. Fig. 6 400 500 600 700 800 900
shows the dispersion characteristics of refractive indices (nx, ny, Wavelength (nm)
nz) for the three crystallographic planes (a, b and c). The dispersion Fig. 6. Plot of refractive index versus wavelength along different planes of MLM
of the refractive indices in the investigated spectral region is trivial crystal.
for normal dispersion that indicates the absence of local absorp- 2
tion bands. An optical material with uniform refractive index is a 100
prime requirement in selecting the materials for the elements of
coherent optics, acousto-optic devices and high-performance 80
Temperature difference (°C/mg)

lenses. Crystal materials with wide optical band gap, better

transparency, low absorbance and low refractive are opted for 0
60
antireflection coating in solar devices and any other optoelectronic
Weight (%)

device fabrications [30]. 40

3.5. Thermal studies 20

-2

Thermal stability and the melting point of the grown MLM can 0
be obtained by TG/DTA measurements and are presented in Fig. 7.
It is seen from Fig. 7 that the decomposition of the sample takes -20
place in three different stages involving dehydration and decom- -4
0 200 400 600 800 1000
position. A sample of weight 2.3860 mg was decomposed during
Temperature (°C)
the first stage over the temperature range from 51.91 1C to 75.25 1C
with a weight loss of 13.37% suggesting that dehydration of water Fig. 7. TG/DTA spectrum of MLM crystal.
 N. Sivakumar et al. / Journal of Crystal Growth 426 (2015) 86–94 91

3.6. Dielectric studies

200

3.6.1. Dielectric permittivity tensor

180
Transport phenomena, defect behavior and structural changes

Dielectric permittivity tensor

of the solid materials can be easily identified by dielectric studies
160
[32]. Temperature as well as frequency effects on dielectric
behaviors of the grown crystals were discussed in the current 140
section. The dielectric permittivity of the monoclinic MLM crystal
is a second-rank tensor with four independent variables. The 120
dielectric properties of a monoclinic crystal may be characterized 70 °C
by the magnitudes and directions along four (ε11, ε22, ε33 and 100 ε11
ε13 ¼ε31) principal dielectric permittivities. The principal axis ‘b’
ε22
always coincides with the two symmetry axis for a crystal with the 80
ε33
monoclinic crystal system and β4 901. The principle independent
variables ε11, ε22, ε33 are parallel to the crystallographic a-, b- and 60
c-axes respectively. 2 3 4 5 6 7
The dielectric permittivity tensor (εij) can be estimated from log f
the expression [33],
Fig. 8. Variation of dielectric permittivity tensor coefficient with frequency.
0 1
ε11 0 ε13
B C
ε ¼ @ 0 ε22 0 A ð6Þ
ε31 0 ε33 120

Among four independent dielectric variables, ε11, ε22 and ε33 can 1kHz
2kHz
be determined by estimating the dielectric permittivity along the 115 3kHz
X-cut (1 0
1), Y-cut (0 1 0) and Z- cut (1 1 1) planes respectively. 4kHz
The area and thickness of the crystal planes used for the dielectric 5kHz
110
measurements on the (1 0
1) plane are 2.47 mm2, 1.4 mm, for
the (0 1 0) plane, 5.56 mm2, 1.77 mm and for the (1 1 1) plane,
3.86 mm2, 1.15 mm respectively. The raw data which were used for 105
the dielectric calculations are given in Tables SM1 and SM2.
Dielectric permittivity can be directly measured using the expres- 100
sion,
C 11;22;33 t
ε11;22;33 ¼ ð7Þ 95
ε0 A
40 50 60 70 80 90
where C11, 22, 33 are the parallel capacitances in farad, A is the area Temperature (°C)
of contact in m2, t is the crystal thickness in m, and ε0 is the
Fig. 9. Dielectric permittivity (ε0 ) versus temperature of MLM crystal at different
permittivity of free space (8.854  10–12 Fm
1). The imaginary part
frequencies.
of the dielectric constant ε″ of the sample is given by ε″ ¼ε0 tan δ.
Frequency dependent dielectric permittivity tensor coefficients
(ε11, ε22 and ε33) are shown in Fig. 8. The tensor components ε11, phase transition. This anomalous dielectric behavior may be due to
ε22 and ε33 show dispersive nature at low as well as at high removal of water molecules or due to the structural changes observed
frequencies which results in anisotropic behavior. Dielectric per- in the crystal. It was reported that the dielectric anomaly observed in
mittivity values for the tensor components ε11, ε22 and ε33 at 70 1C the crystals with centrosymmetric space group P21/c is due to the
are found to be 80, 108 and 118 respectively. The dielectric tensor dehydration of water molecules which is a good polarizable molecule
anisotropy coefficient was calculated for ε11 and ε33 components in the crystal. The water molecules are having little interaction with
using the relation, the crystal surface which prevents the reorientation of molecular
T ¼ Δεr =εr ð8Þ dipoles at temperatures lower than 55 1C. Increase of temperature,
decreases the interaction between the water molecules and the crystal
where Δε0 is the difference in dielectric permittivity values of the surface and thus the water molecules are freely re-orientated. Hence,
two planes (ε11 and ε33) and ε0 is the maximum value of dielectric dielectric constant increases beyond 55 1C and reaches a high value at
permittivity. Anisotropy in dielectric tensor coefficient (T) of MLM about 70 1C. The orientational polarization is possible only if the
crystal was found to be 32.20%. Anisotropy observed in the molecules in the materials associated with an asymmetrical structure.
dielectric permittivity could be the presence of water molecules For water molecules the bonding structure is asymmetrical, hence, a
in the crystal structure and the details are completely discussed in net permanent dipole moment was observed. After the transition
the forthcoming sections. temperature (70 1C), the dielectric permittivity value decreases and is
due to the reduction in orientational polarization by the loss of water
3.6.2. Temperature dependent dielectric permittivity and dielectric molecules. The melaminium levulinate complex contains one lattice
loss water molecule which is responsible for the maximum dielectric
Fig. 9 represents the variation of dielectric permittivity (ε0 ) of MLM constant at 70 1C. From the thermal analysis it is confirmed that the
crystal measured the along (1 0
1) plane corresponding to different water molecules of the complex get away in the temperature range
temperatures at different frequencies in the range (1–5 kHz) of the 51.91–75.25 1C, and accompanied with the decrease of dielectric
applied ac field. From the Fig. 9, it is clear that the dielectric permittivity beyond the transition temperature. As a result, dielectric
permittivity increases with temperature and reaches a maximum permittivity decreases and attains a constant value by the complete
value at 70 1C and beyond 70 1C it starts decreasing. The dielectric removal of water molecules. Thus the presence of water molecules in
anomaly observed at 70 1C in the frequency range 1–5 kHz is due to the crystal boundary has great impact on the dielectric property and
92 N. Sivakumar et al. / Journal of Crystal Growth 426 (2015) 86–94

0.17 dependence of dielectric loss (tan δ) also exhibits a similar type

1kHz
0.17 2 kHz 0.16 of polarization mechanism as exhibited by dielectric permittivity

Dielectric loss (tan δ)

3 kHz 0.15
and is shown in Fig. 11(b). It is well established that the grown
4 kHz 0.14
crystal with less dielectric loss results in a high degree of crystal
0.16 5 kHz 0.13
quality with lesser electrically active defects [40].
Dielectric loss (tan δ)

0.12
0.11
0.15 0.10
40 50 60 70 80 90
3.6.4. Frequency dependent ac conductivity
Temperature (° C) The ac conductivity can be related to dielectric loss tangent as
0.14 σ ac ¼ ωεo ε0 tan δ ð9Þ
where εo and ω are the permittivity of free space and angular
0.13 frequency, respectively.
Fig. 12(a) represents a plot of σac vs. log ω at different
temperatures by which conduction mechanism of MLM crystal
0.12 can be easily analyzed. At lower frequencies, electrical conductiv-
40 50 60 70 80 90 100 110 120
ity is found to be independent of frequency and is called dc con-
Temperature (°C)
ductivity (σdc) of the material. The conductivity in this region is
Fig. 10. Dielectric loss (tan δ) versus temperature of MLM crystal at different attributed to ionic charge carriers undergo a random diffusion
frequencies. process through activated hopping. At higher frequencies, the
electrical conductivity increases with frequency and the variation
obeys Jonscher's universal law [41],
150
1.6 σ ac ¼ σ 0 þ Aωs ð10Þ
1.4 40°C
140 1.2 55°C where ω is the angular frequency, s is the power law exponent and
Dielectric loss (tan δ)

70°C
1.0
85°C σo is the dc conductivity. The power law exponent (s) is a function
130 0.8
0.6 of temperature and ‘s’ lies between 0 and 1 [42]. Fig. 13(a) gives a
0.4 plot of log σac versus log ω for MLM crystal for the temperature
Dielectric constant

120 0.2
0.0
range 40–85 1C. The value of ‘s’ could be determined from the
110 1 2 3 4 5 6 7 slope of the plots and are calculated to be s ¼ 0.79, 0.74, 0.76 and
log f
0.78 for the temperatures 40, 55, 70 and 85 1C respectively.The
100
40°C increasing trend of conductivity with frequency indicates hopping
90 55°C
conduction of protons through hydrogen bonds [43]. As the
frequency increases the conduction hopes will be less in the limit
70°C
80 of interatomic distances and will no longer be randomly distrib-
85°C
70
uted. Hence, the conductivity will settle to frequency dependence
which tends to ωs [44]. The crystals of melaminium levulinate
2 3 4 5 6 7 monohydrate are formed through self-assembled hydrogen bond-
log f ing by cocrystallization of melamine and levulinic acid. The
carboxyl acid group is a proton donor and the melamine is a
Fig. 11. (a) Plot of dielectric permittivity vs log frequency and (b) dielectric loss (tan
δ) vs log frequency of MLM crystal.
proton acceptor. MLM crystal contains protonated melamine at
one of the three ring N atoms. In MLM crystal all H atoms of the
contributes to the anomalous dielectric permittivity [34–36]. The single protonated melaminium residues form N–H…O hydrogen
dielectric loss (tan δ) is also exhibits a same type of variation as bonds. A combination of ionic and donor-acceptor hydrogen bond
observed in the dielectric permittivity and is shown in Fig. 10. For both interactions link the melamine1 þ residues with levulinate ions
dielectric permittivity and loss, in the temperature range 55o and water molecules to form a three dimensional network [14].
To70 1C, more energy is dissipated for reorienting the permanent This arrangement gives a favorable picture of conduction due to
dipoles in the molecule along the applied field direction. It is
concluded from the dielectric study that the dielectric behavior in
such material is almost frequency-independent [37].

3.6.3. Frequency dependent dielectric permittivity and dielectric loss

Fig. 11 shows the dielectric measurements on (1 0
1) plane of
MLM crystal in which both dielectric permittivity (ε0 ) and dielec-
tric loss (tan δ) decreases and reaches a constant value at higher
frequencies. The dielectric behavior of the materials can be easily
explained by the different polarization mechanism like ionic,
electronic, orientation and space charge polarizations. At the
higher frequencies, molecular dipoles cannot deals with the
varying electric field and thus dielectric permittivity decreases
and reaches a constant value [38,39] for the frequency range
100 kHz – 5 MHz. High dielectric value at the low frequencies
reflects the space charge polarization due to the grain boundaries
in the crystal materials. At very high frequencies, the contributions Fig. 12. (a) Variation of ac conductivity versus frequencies at the temperatures
from different polarizations start decreasing and the system (from 40 1C to 85 1C) and (b) Variation of ac conductivity versus temperature at the
unable to adopt any quick applied electric field changes. The frequencies (from 1 kHz to 5 kHz).
 N. Sivakumar et al. / Journal of Crystal Growth 426 (2015) 86–94 93

thermal conductivity of the solid materials can be measured by

Widemann–Franz law using AC electrical conductivity (σac) given
by the relation [50],
k ¼ LσT ð12Þ
where, L is the Lorentz number and can be calculated by the
equation,
π2
L¼ ¼ 2:45  10
8 ð13Þ
3ðkB =eÞ2
The thermal conductivity for the different temperatures 40, 55,
70 1C were calculated and the values are 5.05  10–11, 5.28  10–11
and 5.99  10–11 W/mK respectively. Increase of thermal conduc-
tivity with temperature represents the linear behavior of the
materials and this could be due to the contribution of phonons
as well as electron motion. For cooling purposes, the develop-
ments of efficient heat transfer materials are required. Materials
with low thermal conductivity materials/fluids can efficiently
Fig. 13. (a) Variation of log σac with log ω at different temperatures and
(b) Variation of ln σac with 1000/T at the frequencies 1 kHz, 100 kHz and 2 MHz.
transfer the heat energy and such materials are very limited.
Hence the present material with low thermal conductivity can be
opted for ultrahigh cooling instruments to keep the instrumenta-
proton transfer through H-bonds in MLM crystal. Many hydrogen tion cool for efficient operations [51].
bonded solids show conductivity via proton transfer through
H-bonds [45]. Therefore, MLM crystal can be a protonic conductor. 3.8. Surface laser damage threshold (LDT) measurement

3.6.5. Temperature dependent ac conductivity The exposure of high intense laser light on the crystals plays a
The ac electrical conductivity (σac) study as a function of vital role in NLO devices, electro-optic modulations, production of
temperature was performed on (1 0
1) plane of MLM crystal third harmonic generation etc. which are mainly involves the
and is presented in Fig. 12(b). As the temperature increases, ac capacity to withstand highly intense laser light [52]. LDT measure-
electrical conductivity also increases linearly and it could be due to ments are mainly trust the suggested laser parameters like pulse
the mobility of free charges like free ions and polarons. The rise of duration, laser irradiance, beam size, experimental geometry and
conductivity with temperature and frequency, shows the common repetition rates. Performances of optical crystals under LDT study
response for polymeric and semiconductor samples [46]. The as are limited in the second harmonic generation applications [53].
conductivity is almost constant in the temperature range 40o Hence, in the present case, a single shot laser pulse method was
T o55 1C and reaches a maximum value at 70 1C and starts dec- employed on a well polished MLM crystal to measure the LDT
reasing after this temperature. Increase in conductivity in the value. An actively Q-switched Nd:YAG laser of wavelength
range 55 oTo 70 1C is attributed to the concentration of mobile 1064 nm with 10 ns pulse width was used for LDT measurements.
charge carriers i.e. H þ and OH
ions produced by the dissociation A laser beam size on the specimen was measured to be 1 mm and
of water molecules present in the crystal. This type of conduction a repetition rate of 10 Hz was used in this study. Initially, a power
in the crystal material is known as protonic conduction [47]. The meter attached to LDT setup measures the input laser energy
density of dissociated ions of the water molecules decreases, when density. Controlled output laser intensity was allowed to fall on
the temperature is increased beyond the transition temperature the crystal sample which placed near the converging lens and the
(70 1C). This is attributed to the temperature range 51.91–75.25 1C power density can be calculated using energy (mJ), pulse width
as reported in the thermal analysis of the crystal. (ns) and area (cm2) and are related by the equation,
E
3.7. 6. AC activation energy (Ea) calculation Pd ¼ ð14Þ
τA
The activation energy of crystals at a given frequency can be esti- where E is the energy (mJ), τ is the pulse width (ns) and A is the
mated by temperature dependent ac conductivity. Fig. 13(b) shows a area of the circular spot size. Single shot LDT value of MLM crystal
plot of ln σac vs. 1000/T from which activation energy (Ea) can be is found to be 2.84 GW/cm2 which comparatively greater than the
estimated using the relation [48], standard materials KDP and urea, whose LDT values are 0.2 GW/
  cm2 and 1.5 GW/cm2 respectively [54]. Hence, the grown MLM
Ea
σ ac ¼ σ 0 exp ð11Þ crystal with large LDT value can be used for high-power laser
KT
device fabrications to withstand high laser intensity.
All the parameters in the above equation are having their usual
meanings. Activation energies (Ea) can be evaluated from the slope of
the straight lines (plot of ln ac vs. 1000/T) using the relation, Ea ¼ 4. Conclusion

slope  1000  k. The measured values are 0.1404, 0.0913,
0.08262 eV for the frequencies 1 kHz, 100 kHz and 2 MHz, respec- Bulk crystal of the melaminium levulinate monohydrate (MLM) is
tively. Low activation energy values reveal that the grown crystal obtained by the slow solvent evaporation method. The molecular
possesses lesser defects and can be used for device fabrications [49]. structure was elucidated using FT-IR spectral analysis. UV–vis spec-
trum of MLM crystal reveals good optical transparency with lower
3.7.1. Thermal conductivity calculation cut-off wavelength at 293 nm and the direct band gap is calculated to
Many high temperature/power optoelectronic devices are be 4.20 eV. The refractive indices for the planes (1 0
1), (0 1 0) and
depend on thermal conductivity and which is also considered as (1 1 1) are also calculated. MLM crystal exhibits thermal stability up
one of the most important properties for laser materials. The to 130 1C and its melting point temperature is found to be 185 1C.
94 N. Sivakumar et al. / Journal of Crystal Growth 426 (2015) 86–94

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