Journal of Minerals & Materials Characterization & Engineering, Vol. 6, No.1, pp 17-24, 2007
jmmce.org Printed in the USA. All rights reserved
17
Crystal Growth of Some Rena l S tones Constituents: I. In vitro
Crystallization of T ra c e E l e m en t an d It s Ch a r ac t e r ization Studies
P. Sundaramoorthi and S. Kalainathan*
Department of physics, Mahendra Engg College, Mallasamuduram, Namakkal,
TamilNadu, India-637503. ()
*Department of Physics, Vellore Institute of Technology, Deemed University Vellore,
India.
Abstract
The urinary calculi formation is still now unknown problems and seems to be very
complex phenomenon. The in vitro studies are carried out by artificial renal stone
formation in silica gel medium. In general, it appeared that trace element (TE) contents
in mixed structure are always between values of respective pure phases. It is also found
that some of the toxic elements such as barium are related to the structure but not
necessarily to environment influences as in the case of lead. Barium hydrogen phosphate
crystals are grown in gel method then identified the optimum growth parameters. TE
mixed crystals are grown in different growth parameters. The grown crystals are
analyzed by XRD, TGA/DTA, and SEM.The results are recorded and reported.
Key words- Renal stones, TE-BHP, renal calculi, gel growth, Surface morphology,
Growth parameters, trace elements, SDM, DDM.
1. INTRODUCTION
A trace element (TE) with the organic, semi organic and organic mixed mineral
deposition in urinary tract is less frequent in human history. Strontium hydrogen
phosphate stones account for less than 5% of all urinary stones [1], but occur in
individuals with rare genetic disorder in a renal tubular transport system. The defective
absorption of organic and inorganic minerals in renal tubular system called Fanconi
syndromes is believed to exist in associated with the mineral deposition in the renal
systems. Renal stone (RS) diseases are due to biomineralisation. RS grows in a gel like
medium, which is why they have radially striated growth [2]. The crystal growth by gel
methods, provide to simulation of synovial cartilage and biological fluids [3]. The gel
growth [in vitro study] of some urinary stone constituents COM, COD, CHP, HAP and
the inhibitory role are reported [4]. Still there is no such an exact evidence to grow the
trace element mixed RS [in vitro and in-vivo] growth. These types of TE-RS are in less
percentage available within the urinary tract deposition. However, the TE-RS types
produce major toxic effect in the urinary tract and induce human pathological causes. In

18 P. Sundaramoorthi and S. Kalainathan Vol.6, No.1
BHP crystal, barium is a toxic element, which may be absorbed in three ways. One is via
air- by breathing. The average consumption rate is one microgram per day. The second is
via liquid -by liquid /water in take. The average consumption rate was 1-20 micrograms
per liter. The third one is via solid-by food intake. The average consumption of barium
present is 600-900 micrograms per day. For a normal man, the barium consumption bar
limit is 1240 micrograms per day, which is the tolerance level, if exceeds the specific
tolerance level of human physical system, automatic RS deposition occurs. Authors have
grown different RS crystals in several series of experiments with silica gel at different pH
values. The dissociation of phosphoric acid system can be represented by three-
dissociation equilibrium and the presence of various ions at various pH values are
reported [5]. Because of these results, the gel pH in the range from 5.5 to 11 has been
used (Milwaukee QS-MN pH-600, packet digital pH-meter are used for measurements) in
which the HPO42- ions dominates or alone exist. This decreases the possibility of BMP
crystals occurring during the BHP growth.
2 EXPERIMENTAL STUDY (CRYSTALLIZATION)
The crystallization apparatus employed are glass test tube of 25 mm diameter and 150
mm long for single diffusion method (SD) and. thick walled 30 mm diameter and 180mm
long glass U tubes for double diffusion (DD) method. The chemicals used are Excelar-
Qualigens (E-Q) AR grade BaCl2 (MW-244.28) and E-Q, AR grade orthophosphoric acid
(Sp.gr.1.75). The SMS gel or water glasses are prepared as per the literature [6] .The
reactant orthophosphoric acid is mixed with silica gel at desired gel density and elevated
temperatures. After the gel set, the supernatant mixture (Barium chloride) at a required
mole solutions are slowly added along the walls of the growth columns (test tubes, U-
tubes) over the set gels, then tightly closed to prevent evaporation. The growth systems
are allowed to react within the gel medium and the following chemical reaction takes
place.
BaCl2 + H3PO4 + gel Æ BaHPO4 + by products.
The crystal growth experiments are carried out at room temperature (average of 290C.
3. RESULT AND DISCUSSION
3.1 The following observations have been made in the present work.
1. The reaction starts immediately after the addition of supernatant solutions. However,
the nucleation is observed only after 14 hours and the growth process took a period of
two to three months for completion.
2. Leaf shape crystals, fiber and dendrites are observed along with Lies gang rings in the
first half of the gel column from the top of the test tube.

Vol.6, No.1 Crystal Growth of Some Renal Stones 19
3. Some well-developed single crystals are observed in the DD growth columns (U-tubes)
after one month. The growth processes are allowed for six months but the crystal size
did not increase.
4. The gel density above 1.07g/cm3 and with pH above 9 yielded no crystals, but mean
time reaction takes place.
5. Some of the test tubes of gel density 1.03g/cm3 with pH around 7 and below 7 are
allowed for the reactions to take place. After a period of six months, a less number of
nucleation were observed near the bottom of the test tubes. Some of them grew in
needle and well transparent platelet crystals.
6. From the investigation, the optimum growth parameters of BHP crystals are identified
and reported in Table-1, 2.
7. An extension of the reaction period at up to ten months did not improve the size of
these crystals.
8. The growth columns of BHP crystals are shown in the Fig-1, 2
9. Some of the harvested BHP crystals are shown in the Fig-3-4.
10. The maximum dimension of the crystals obtained is 3 mm x 5 mm x 6 mm.
3.2 X-ray studies of BHP crystals.
The crystals of BHP are dried and used for analysis. X-ray diffractograms (XRD) are
recorded using Siemens X-ray diffaractometer with CuKα.-Radiation (wave length
1.5418Å). The single crystal XRD of grown BHP matched well with the chemical
crystals database. The lattice parameters are a=10.0115Å, b=10.2089Å, c=10.677210Å,
α=90.0031˚, β= 90.0257 ˚, γ=90.0050˚. From this data, the BHP crystal system is triclinic
[7, 8].
3.3. Thermo gravimetric (TGA and DTA) analysis of BHP crystals.
The TGA and DTA of BHP crystals are carried out by STA 11500-PLTS instruments.
The BHP crystals of 2.439mg sample are taken to the TGA process. The TGA are started
from room temperature to 10000 C by heating at a constant rate. Fig.5, shows the TGA
and DTA graph of BHP crystals. The percentages of weight present in the BHP sample
at a particular temperature are tabulated in Table- 3 [9].
The TGA results show BHP crystals are decomposed (67.9%of samples) at temperatures
up to 453 0C due to the presence of hydrogen and phosphorus with oxygen atoms. Above
the temperature, the remaining samples are stable up to the end of the analysis.
The expected chemical reactions
BaHPO4.XH2O ▲ BaHPO4 + X H2O (Vapour)
2BaPO4 ▲ 2 Ba + P2O4 (Vapour)
Barium is a stable compound with respect to the temperature up to 1230 0C (melting
point). About 67.9% of the BHP crystals by weight are evaporated and the remaining
32.1% of the samples are stable at temperatures up to 1000 0C.

20 P. Sundaramoorthi and S. Kalainathan Vol.6, No.1
Table-1 Single diffusion (SD) growth process. (Reaction test tubes)
Growth parameters.
Gel
density
gm /cc3
Phosphoric
acid
concentration
(Inner reactant
mixed with
gel)
Gel+
HPO4
pH
value
Gel setting
time
Supernatant
Concentration
Bacl2
(M)
Nucleation
observed in
hrs
Growth
period
in days
Growth
appearances
Inside the
growth
medium
1.03
1.03
1.03
1.03
1N
1N
1N
1N
6.4
6.8
6.9
7.1
26 hrs
16 hrs
6 mins.
18 hrs
1
-do-
-do-
-do-
16 hrs
17 hrs
32 hrs
89 hrs 136 SC, PC
1.03
1.03
1.03
1.03
1.5N
1.5N
1.5N
1.5N
6.6
6.7
7.1
8.0
28 hrs
1 hrs
3 hrs
46 hrs
-do-
-do-
-do-
-do-
26 hrs
16 hrs
46 hrs
66 hrs
90
SC
1.04
1.04
1.04
1.04
1 N
1 N
1 N
1 N
6.3
6.8
6.9
7.4
34 hrs
6 hrs
45 min
68 hrs
-do-
-do-
-do-
-do-
14 hrs
22 hrs
28 hrs
68 hrs
140 SC,PC
1.04
1.04
1.04
1.04
2N
2N
2N
2N
6.6
6.8
7.1
7.5
24 hrs
1 hour
12 hrs
48 hrs
-do-
-do-
-do-
-do-
13 hrs
14 hrs
24 hrs
72 hrs
75 SC
SC- Good transparent single crystals are observed.
PC-Poly crystals are observed.

Vol.6, No.1 Crystal Growth of Some Renal Stones 21
Table-2. Double- diffusion (DD) growth process. (U- tubes)
Growth parameters
Gel
density
gm /cc3
Phosphoric
acid
concentration
(Inner reactant
mixed with
gel)
Gel+
HPO4
pH
value
Gel setting
time
Supernatant
Concentration
Bacl2
(M)
Nucleation
observed in
hrs
Growth
period
in days
Growth
appearances
Inside the
growth
medium
1.05
1.05
1.05
1.05
1 N
1 N
1 N
1 N
6.0
6.7
6.9
7.1
48 hrs
16 hrs
15 Mts.
26 hrs
1
-do-
-do-
-do-
45 hrs
26 hrs
22 hrs
90 hrs
90 SC
1.05
1.05
1.05
1.05
2N
2N
2N
2N
6.4
6.9
7.2
8.1
36hrs
4 hrs
1 hrs
98 hrs
-do-
-do-
-do-
-do-
20 hrs
22 hrs
86 hrs
98 hrs
70 SC, PC
1.04
1.04
1.04
1.04
1 N
1 N
1 N
1 N
6.2
6.8
7.2
7.6
46 hrs
5 hrs
30 mts
28 hrs
-do-
-do-
-do-
-do-
40 hrs
22 hrs
64 hrs
88 hrs
110 SC
1.04
1.04
1.04
1.04
2N
2N
2N
2N
6.2
6.9
7.5
7.9
88 hrs
1 hour
10 hrs
58 hrs
-do-
-do-
-do-
-do-
20 hrs
15 hrs
32 hrs
82 hrs
90 SC, PC
SC-good transparent single crystals are observed.
PC-Poly crystals are observed

22 P. Sundaramoorthi and S. Kalainathan Vol.6, No.1
.

Vol.6, No.1 Crystal Growth of Some Renal Stones 23
Table 3. Thermal Analysis of BHP crystals
TGA Point
s Temperature
º C
% Of BHP crystal present
DTA in 0C
1
2
3
4
5
35
131.50
199.76
452.24
850
100
101.24
74.95
67.941
67.9
128.47
182.53
249.77
669.10
691.28
3.4. Scanning Electron Microscopy study of BHP crystals
Well-grown BHP single crystals are selected for the investigation of surface morphology
crystal by using SEM. The SEM photographs are taken in the version S-300-I instrument.
The sample named as VCA-600 kept in lobe middle; the data size are 640 x 480
micrometer. The minor (minimum) and major (maximum) magnification of SEM was
about 250 times. SEM acceleration voltage is 25000 volts and kept the sample in highly
vacuumed. 18200-micrometer working distance and monochromatic color mode are
employed. 100µmeter focusing of BHP crystal SEM is shown in the Fig-6. The surfaces
of the BHP crystal are smooth, few valley patterns are observed in the crystal plane [10-
13].

24 P. Sundaramoorthi and S. Kalainathan Vol.6, No.1
Conclusion
The BHP RS constituents are crystallized by single and double diffusion methods in
sodium meta silicate gel. The single crystal XRD studies confirmed the structural identity
of grown BHP single crystal. The TGA/DTA studies are carried out, and then calculated
the losses of weight of the BHP crystals versus temperature up to 9000C. The BHP
surface morphology is identified by SEM studies.
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