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Journal of Taibah University for Science 11 (2017) 540–547
Abstract
A simple preconcentration method for zirconium based on coprecipitation with aluminium hydroxide prior to flame atomic
absorption (FAAS) determination was established. The recovery values of the analyte ions were higher than 95%. Such parameters
as the type of hydroxide ion source for precipitation, type of acid for the dissolution step, amount of Al3+ ion as the collector,
pH, temperature, standing time and centrifuge time were optimized using 50 mL of a solution containing 150 g of zirconium.
The effect of the solution volume and influences of matrix ions on the extraction of the analyte were also examined. Under the
optimum conditions, the calibration curve was linear up to 10 mg L−1 . The relative standard deviation for solutions containing
150 g of zirconium was found to be 3.9%. The limit of detection (LOD) and limit of quantitation (LOQ) were calculated as 0.17
and 0.57 mg L−1 , respectively. The method is capable of extracting the analyte in different samples with volumes of up to 250 mL.
The preconcentration factor for 250 mL and enhancement factor for 50 mL of analyte solution were calculated to be 250 and 40,
respectively. The proposed method was successfully applied for the determination of zirconium in glass and refractory brick samples.
© 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Keywords: Coprecipitation; Zirconium; Aluminium hydroxide; Refractory bricks; Glass; Atomic absorption spectrometry
1. Introduction The word zircon comes from the Persian word zargun
meaning “gold-coloured” [1]. Zirconium is a corrosion
Zirconium is the second element of group 4B. This resistant metal, and it is used in high performance pumps
element’s name is taken from the name of the mineral zir- and valves. Because it also does not easily absorb neu-
con (ZrSiO4 ), the most important source of zirconium. trons, zirconium is widely used in nuclear reactors.
Zirconium is superconductive at low temperatures and is
used to make superconductive magnets, which offer the
∗ Corresponding author. Tel.: +98 7433223048; possibility of realizing the direct large-scale generation
fax: +98 74133223048.
E-mail address: ashokrollahi@mail.yu.ac.ir (A. Shokrollahi).
of electric power [2].
Peer review under responsibility of Taibah University. Zirconium dioxide (ZrO2 ) is one of the most studied
ceramic materials. It can withstand very high temper-
atures and is used to make crucibles, refractory bricks
and to line the walls of high temperature furnaces. Fused
cast AZS (alumina, zirconia, silica) and AZCS (alumina,
http://dx.doi.org/10.1016/j.jtusci.2015.11.006
1658-3655 © 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
A. Shokrollahi, M. Gohari / Journal of Taibah University for Science 11 (2017) 540–547 541
In order to achieve an acceptable recovery, the effects The influence of the pH of the sample solution on the
of variables that may have a significant influence on the recovery of zirconium was investigated in the pH range
coprecipitation, dissolution and atomic absorption sig- of 5.0–10.0 by adjusting the pH value of the solution with
nal, such as the hydroxide ion type, type of acid solvent, the addition of different amounts of a 5% ammonia solu-
pH, amount of collector, standing and centrifuge time, tion. As shown in Fig. 1, zirconium was quantitatively
temperature, volume of sample, and interfering ions, coprecipitated in the pH range of 7.0–9.0. The decrease
were examined. in the signal at pH values >9.0 is due to the dissolution of
the precipitate as Al(OH)4 − in highly alkaline solutions.
3.1. Effect of the hydroxide ion source In order to achieve a high efficiency and good selectiv-
ity, a pH of approximately 8 was selected for all of the
The coagulation step is a very important factor for subsequent coprecipitation experiments.
achieving a quick coprecipitation and the easy sepa-
ration of the coprecipitate from the supernatant with 3.4. Effect of the amount of Al3+ ion
a simple separation procedure. A high recovery of the
analyte and good reproducibility are also related to the The amount of collector is very important and must
coprecipitation conditions; therefore, initial studies were be optimized. A sufficient amount of collector must
performed with different bases such as ammonia (NH3 ), be added to the sample solution to ensure the perfect
soda ash (Na2 CO3 ), caustic soda (NaOH) and caustic coprecipitation of the analyte; in contrast, the amount
potash (KOH) with recoveries of 104%, 95%, 97%, and of collector must be small to limit the final volume.
97%, respectively. Because ammonium ion increases the Therefore, the influence of the amount of Al3+ ion
signal of Zr [44], it was selected as the hydroxide ion as the collector on the recovery of zirconium was
source in the coprecipitation procedure. investigated in the range of 0–3.0 mg. The results are
depicted in Fig. 2. Acceptable recovery values were
3.2. Effect of the acid type as the solvent obtained in the range of 1.0–2.5 mg of Al3+ ion. In
lower amounts, the collection is incomplete, and with
HF, HClO4 , HNO3 , and HCl were used for the disso- higher amounts of collector, the high concentration of
lution of the precipitate. Due to the high concentration collector in final solution and high viscosity of the final
A. Shokrollahi, M. Gohari / Journal of Taibah University for Science 11 (2017) 540–547 543
Fig. 2. Effect of the amount of Al3+ ion on the recovery of the analyte: Fig. 4. Effect of the temperature on the recovery of the analyte: 150 g
150 g of zirconium, different volumes of Al (1000 mg L−1 ), pH = 8, of zirconium, 2 mg of Al3+ ion, pH = 8, initial volume of 50 mL, at
initial volume of 50 mL, at 25 ◦ C. different temperatures.
solution limit the absorption signal. Consequently, all solubility of the precipitate in acidic medium decreased,
further investigations were performed with 2 mg (2 mL and a viscous fluid was formed after the addition of acid.
Al3+ 1000 mg L−1 ) of Al3+ ion. According to the litera- The effect of the temperature on the coprecipitation
ture [43], 0.2% of Al3+ ion is needed for increasing the was also examined in the range of 25–70 ◦ C. As seen
zirconium signal in atomic spectrometry. In this case, the in Fig. 4, quantitative recovery was obtained at room
selected value for the collector in the final solution con- temperature. A viscous solution was formed after the
forms to this value for the Al3+ ion, which is proposed dissolution of the precipitate, which had been formed in
for increasing the zirconium absorption signal in flame high temperatures similar to the case of a long standing
atomic absorption spectrometry. time. A low aspiration efficiency of the viscous solution
and, consequently, a low atomization efficiency in FAAS
3.5. Effects of the standing time, temperature and would be the reasons for the decreasing absorption signal
centrifugation time at high temperatures and long standing times. Thus, room
temperature was selected for all of the experiments.
The standing time, which is important for the quality The centrifugation time was also optimized within the
of the coprecipitation, was evaluated at different times in 1–15 min time period with centrifugation at 4000 rpm.
the range of 0–6 h at room temperature. The results are The required centrifugation time for the successful
shown in Fig. 3. Quantitative recovery was found after coprecipitation with quantitative recovery of the analyte
the formation of the precipitate, and further contact time was determined to be at least 2 min, but in order to obtain
did not lead to better recovery; therefore, no standing a more compact precipitate, a time of 5 min was chosen
time was considered for the following experiments, and for all subsequent coprecipitation experiments.
phase separation was performed after adjustment of the
pH. It must be noted that for standing times above 4 h, the 3.6. Effect of the sample volume
Table 1
Effects of diverse ions on the zirconium recovery under the following conditions: 150 g of zirconium, 2 mg of Al3+ ion, pH = 8, initial volume of
50 mL, at 25 ◦ C.
Ion Recovery (%) Concentration (mgL−1 )
NH4 + , Na+ , K+ , Ca2+ , Ba2+ , B3+ (as H3 BO3 ), OAC− , 105, 101, 97, 95,97, 95, 95, 1000
NO3 − , Cl− , Br− , I− , MoO4 2− 99, 98, 95, 105,97
Mg2+ , Zn2+ , Fe3+ , Al3+ , Cr2 O7 2− , SiO3 2− , SO4 2− , F− 97,96, 95, 99, 96,95, 95, 99 100
Cu2+ , Ni2+ , Mn2+ , Ti4+ (dissolved TiO2 ), PO4 3− 95, 96, 96, 98, 95 10
applied a 50 mL sample volume for all optimizations and 3.8. Analytical performance
determinations.
An Abs vs. concentration calibration graph was
plotted after the coprecipitation of 50 mL of standard
3.7. Interference studies solutions under the optimum experimental conditions.
The graph was linear up to 10 mg L−1 . The equation of
In order to assess the possible analytical applications the calibration graph was y = 0.0243x + 0.003 with a cor-
of the presented coprecipitation procedure, the effects relation coefficient of 0.9991. The detection limit (LOD)
of some foreign ions that ordinarily exist in various real and limit of quantitation (LOQ) under the optimal exper-
samples were examined under the optimized conditions. imental conditions for ten blank solutions and based on
The recovery of the analyte was generally higher than three times the standard deviation of the blank were
95%. A tolerable limit was defined as the highest amount found to be 0.17 and 0.57 mg L−1 , respectively. The pre-
of foreign ions that produce an error not exceeding 5% cision of the method was evaluated under the optimum
in the determination of the analyte by the coprecipitation conditions. For this purpose, the procedure was repeated
method. The tolerable levels of NH4 + , Li+ , Na+ , Ca2+ , ten times with 50 mL of solution containing 3 mg L−1
Mg2+ , Cr2 O7 2− , and B3+ ions are suitable for the sep- zirconium. The relative standard deviation was calcu-
aration and preconcentration of zirconium in glass and lated to be 3.9%. The preconcentration factor, which is
refractory brick samples (Table 1). the ratio of the initial volume to the final volume, was
Table 2
Zirconium determination in refractory brick samples (n = 4).
Sample Added (mg L−1 ) Found (mg L−1 ) Recovery (%) Value in sample (ZrO2 %) Accepted
value (ZrO2 %)
Table 3
Comparison of the characteristics of the presented method for zirconium determination with those of some previous methods.
Method LOD (mg L−1 ) RSD (%) Dynamic range (mg L−1 ) Enhancement factor Ref
calculated as 250 for 250 mL of analyte solution. atomic absorption spectrometry. This method can be
Because the equation of calibration graph for the direct recommended for the routine analysis of zirconium in
signal of zirconium was y = 0.0006x + 0.003 with a cor- geological and industrial samples, especially refractory
relation coefficient of 0.9992, the enhancement factor, bricks as well as water and biological samples. Under the
which is calculated by dividing the slope of the cali- optimum experimental conditions, quantitative recovery
bration curve with coprecipitation by the slope of the was achieved with a preconcentration factor of 250.
calibration curve without coprecipitation, was calculated Merit numbers of the presented method have been
to be 40 for 50 mL of analyte solution. Sample through- compared with those of some previous methods for
put was also found to be 12 samples h−1 . the determination of zirconium. As shown in Table 3,
although the limit of detection of the proposed method is
3.9. Application to real samples higher than those of all of the reported methods, the RSD
of the presented method is better than those of some of
The proposed method was applied for the determina- the other methods [32] and is comparable to that of spec-
tion of zirconium in AZS and AZCS refractory bricks trophotometry [25]. Additionally, the dynamic range of
as well as glass samples produced in a furnace with the proposed method is broader than that of stripping
AZS and AZCS refractory bricks in its paving and walls. voltammetry [19] and is comparable to that of ICP-AES
As shown in Table 2, the recoveries of spiked sam- (liquid extraction) [22]. This method also has a good pre-
ples are acceptable, and there is satisfactory agreement concentration factor compared with all of the methods
between the results obtained by the presented method reported in Table 3.
and accepted values, suggesting that the coprecipitation
procedure is suitable for analysing the zirconium content Acknowledgements
in refractory bricks, glass, and related materials.
We gratefully acknowledge the support of Yasouj
4. Conclusions University for this study. We also acknowledge the Iran
Glass Wool Company for assistance with this research,
Due to the low sensitivity for the determination of especially for preparing the zirconia-containing bricks
zirconium by flame atomic absorption spectrometry, and glass samples.
a preconcentration step prior to the determination is
needed for most samples, such as silicate glass. Copre-
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