Journal of Crystal Growth 218 (2000) 323}326

Growth, thermal and microhardness studies of single crystals of

potassium penta borate (KB5)
K. Thamizharasan , S. Xavier Jesu Raja
, Francis P. Xavier
, P. Sagayaraj
*
Department of Physics, Sir Theagaraya College, Chennai-600 021, India

Department of Physics, Loyola College, Chennai-600 034, India
Received 8 February 2000; accepted 8 May 2000
Communicated by M. Schieber

Abstract

Single crystals of potassium penta borate (KB5) exhibit interesting non-linear optical properties such as phase-
matched second-harmonic generation of the light for a wavelength as short as 216.8 nm. In the present work, single
crystals of KB5 with dimensions upto 20;20;8 mm are grown by slow evaporation method and subjected to X-ray,
TGA, DSC and microhardness studies. The thermogravimetric analysis con"rms the decomposition of KB5 taking place
in two stages. The DSC curve of KB5 crystals are recorded in the temperature range 50}5803C. The phase transition
temperatures and enthalpies of KB5 were measured and the results are discussed. The grown crystals of KB5 are
subjected to microhardness studies using a Vickers diamond pyramid indentor. The microhardness measurements
carried out on the (0 1 0), (1 0 0) and (0 0 1) orientations con"rm the anisotropic nature in the microhardness number
values.  2000 Elsevier Science B.V. All rights reserved.

Keywords: Potassium penta borate single crystals; TGA; DSC; Microhardness

1. Introduction a"1.1065 nm, b"1.1171 nm and c"0.9054 nm.

Recent research on e!ective non-linear optical
materials reveals that borate compound materials
are superior to other commonly used NLO mate-
rials for UV applications [1]. Potassium penta bor-
ate (KB5) is an important inorganic NLO crystal
and it is successfully used for conversion of laser
radiation to the UV and vacuum UV wavelength
region [2,3]. KB5 is a positive biaxial crystal be-
longing to the orthorhombic crystal system with
point group mm2 [4]. The lattice parameters are
* Corresponding author.
A number of research articles have been published
in the literature discussing the growth and NLO
properties of KB5 crystals [5}9]. Twinning in KB5
crystals was observed by Voitsekhovskii et al. [6].
Experiments conducted by Kato con"rmed the "fth
harmonic generation for KB5 crystals at room tem-
peratures, whereas the other NLO crystals like
ADP and KDP can achieve the same only at
high temperature [10]. Umemura and Kato
have achieved sixth-harmonic generation of the
Nd : YAG laser frequency at 1.0642 lm in KB5
crystals by mixing the fundamental and "fth har-
monic at room temperature [11]. A study of the
far-IR re#ectivity spectra of KB5 was done by

0022-0248/00/$ - see front matter  2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 0 0 ) 0 0 5 1 1 - X
324 K. Thamizharasan et al. / Journal of Crystal Growth 218 (2000) 323}326
Miniewiez et al. [12]. The manifestation of hydro-
gen bonds in Raman spectra of KB5 was carried
out by Fedorava et al. [3]. Poprawski et al. have
reported pyroelectric properties of KB5 crystals in
the temperature range of 4.2}430 K [8]. The pres-
sure-induced polarization changes, spontaneous
birefringence and linear electro-optic e!ect are also
reported [8]. In this paper we report the crystal
growth, morphology, powder X-ray di!raction
(XRD), and for the "rst time TGA, DSC and micro-
hardness studies of KB5 crystals.
2. Experimental results and discussion
2.1. Growth of KB5 crystals
Appropriate amount of K CO and H BO
   
were used to prepare the solution KB O ) 4H O
  
(KB5) by continuous stirring, the condition of
super saturation was achieved. The yield was found
to be good and homogeneous. The product was
puri"ed by repeated recrystallizations, typically
thrice, from double-distilled hot water. In order to
ensure the purity of the product, powder XRD
patterns were recorded after completion of every
synthesis and analyzed for di!erent mixed phases.
This super saturated solution was kept in a con-
stant temperature bath at 305 K in a polyethylene
container with a stirror made of the same material.
Crystals prepared by spontaneous nucleation were
used as seed crystals. The crystals were grown by
slow and controlled evaporation of the solvent in
the constant temperature bath. The period of
Fig. 1. Photograph of polished section of the KB5 Crystals.
growth ranged from 60 to 90 days. In the present
work, good size and optical quality crystals of KB5
with dimensions upto 20;20;8 mm are conve-
niently grown in a period of 3 months. Fig. 1 shows
the photograph of one as grown with a polished
section of a single crystal of KB5. The crystals
are nonhygroscopic and optically transparent. The
cleavage is perfect along the (0 1 0) plane and more
di$cult on the (1 0 0) plane [13]. During the growth
experiments few twinned crystals of KB5 were also
seen along with the untwinned crystals. The scheme
of formation of twinned concretion of KB5 crystals
is reported elsewhere [5,6].
2.2. X-ray studies
The powder X-ray analysis of KB5 crystals were
carried out using an X-ray di!ractometer model
Rich. Seifert, XRD 3000P with monochromatic
nickel "ltered Cu K , (j"0.15406 nm) radiation.
?
The sample was scanned over the range 10}603 at
the rate of 13 per min. The input voltage and
current were 35 kV and 30 mA and the slit width
was 0.1 mm. The observed and calculated d values
for di!erent 2h values along with their indices and
relative experimental intensities were measured.
The X-ray powder data was analysed using the
indexing programme TREOR and the calculated
lattice parameters are a"11.020#0.006 As , b"
11.115#0.004 As and c"9.019#0.005 As , which is
found to be in good agreement with the reported
values [14,15].
2.3. TGA and DSC studies
The thermogravimetric analysis (TGA) spectrum
of KB5 crystal was taken using the instrument
`Delta Series TGA 7a. Samples of KB5 initially
weighing 8.305 mg were taken in an alumina cru-
cible and it was heated at a scanning rate of
203C/min from 50 to 8603C. The di!erential scann-
ing calorimetry (DSC) was carried out using the
instrument `Perkin-Elmer, Delta series DSC 7a in
the present investigations. A sample of weight
14.864 mg was taken and heated at the rate of
203C/min from 50 to 5603C. Di!erential scanning
calorimetry (DSC) is an important method for
investigating crystal phase transitions and their
 K. Thamizharasan et al. / Journal of Crystal Growth 218 (2000) 323}326
Fig. 2. DSC curve of KB5 Crystals.
thermal properties. The DSC carried out in the
present investigations is shown in Fig. 2. The com-
pound is stable and there is no phase transition
upto 1623C and after that one distinct anomaly of
heat #ow is observed at 207.193C. The phase
transition of the "rst-order type is accompanied by
large thermal e!ect and the measured enthalpy is
equal to 495.38 J/g. The "rst endothermic corres-
ponds to the loss of 3 moles of H O * a result

which is in good agreement with the reported
values [7]. The DSC curve also indicates a `weaka
exothermic change taking place at a transition tem-
perature of 4503C * which corresponds to the
release of the remaining one mole of crystal water
* results in anhydrous salt. The TGA curve (Fig. 3)
con"rms the two-stage thermal decomposition of
KB5 crystals, and the percentage of weight loss
during the "rst and second stages are 20.54 and
4.46%, respectively.
2.4. Microhardness studies
Microhardness measurements were made using
a Leitz microhardness tester "tted with a diamond
pyramidal indentor. Single crystals of KB5 cut in
325
di!erent orientations (0 1 0, 1 0 0 and 0 0 1) were
ground using silicon carbide powder and acetone,
then polished using a disc polisher and cleaned
using acetone. The applied load varied from 5 to
50 g for a constant indentation period of 10 s. The
diagonal of the indentation marks were measured
using a Leitz Matallax II microscope with a calib-
ration ocular at 500;magni"cation. For a given
load, an average of atleast "ve impressions were
recorded and the diagonal length d was calculated.
The Vickers hardness number H is calculated us-

ing the relation,
H "1.8544 P/d kg mm\, (1)

where P is the applied load in kg and d the mean
diagonal length in mm.
The values of H calculated using Eq. (1) for

a load 5 g on (0 1 0), (1 0 0) and (0 0 1) planes of KB5
crystal is presented in Table 1. The hardness experi-
ments conducted with higher loads reveal that the
H value remains a constant. It is found that the

(0 1 0) cleavable plane is harder than the other two
planes, which con"rms the anisotropic nature in
the hardness number values.
326 K. Thamizharasan et al. / Journal of Crystal Growth 218 (2000) 323}326

Fig. 3. TGA curve of KB5 Crystals.

Table 1 References
Hardness data for KB5 crystals
[1] P. Becker, Adv. Mater. 10 (1998) 979.
Orientation Hardness number H in kg mm\ [2] Kechen Wu, Chuangtian Chen, Appl. Phys. A 54 (1992) 209.

(for a load of 5 g) [3] E.N. Fedorava, A.P. Elisev, L.I.T., Isaenko, Appl. Spectro-
sc. 55 (1991) 867.
010 82.52 [4] V.G. Dmitriev, C.G. Gurzadyan, D.N. Nikogosyam, Hand
100 64.35 book of Non-linear Optical Crystals, Springer, Berlin,
001 78.70 1990, p. 95.
[5] V.N. Voitsekhovskii, V.P. Nikolaeva, I.A. Velichko, Sov.
Phys. Crystallogr. 27 (1982) 585.
[6] V.N. Voitsekhovskii, V.P. Nikolaeva, I.A. Velichko, Sov.
Phys. Crystallogr. 27 (1982) 322.
[7] C. Ramachandra Raja, R. Gobinathan, F.D. Gnanam,
3. Conclusion Crystal Res. Tech. 28 (1993) 453.
[8] R. Poprawski, E. Pawlik, S. Matyjasik, B. Kosturek, Fer-
roelectrics 158 (1994) 103.
In the present study, single crystals of KB5 are
[9] Xue Dong Fing, Zhang Siyvan, Phys. Stat. Sol. B 200
conveniently grown by slow evaporation method. (1997) 351.
DSC and TGA techniques clearly show that KB5 [10] K. Kato, Opt. Commun. 19 (1976) 332.
crystal undergoes a two-stage thermal decomposi- [11] N. Umemura, K. Kato, Appl. Opt. 35 (1996) 5332.
tion, the "rst-order phase transition at 207.193C [12] A. Miniewiez, Y. Marqueton, R. Poprawski, Spectro Chim.
Acta 49-A (1993) 387.
and a rather `weaka second-order at 4503C. The
[13] J.A. Paisner, M.L. Spaeth, D.C. Gerstenberger, Appl. Phys.
microhardness studies on KB5 crystals indicate the Lett. 32 (1978) 476.
anisotropic nature of hardness values for di!erent [14] Harry J. Dewey, IEEE J. Quantum Electron. 12 (1976) 303.
orientations. [15] W.R. Cook, H. Ja!e, Acta Crystallogr. 10 (1957) 705.