LEAD CHROMATE

BY MEETKUMAR WAGHELA
AIM

◂ To Prepare Lead chromate (PbCrO4)

2
EQUATION

3
What is lead chromate used for?

◂ It is used as a pigment in oil and watercolor

paints, and in ceramics, rubber and plastics,
and fabric printing.

4
STRUCTURE

5
Applying the Taguchi Robust Design
to Optimization of the Experimental
Conditions for Synthesis of Lead
Chromate Nanorods

Seied Mahdi Pourmortazavi

6
 INTRODUCTION
◂ The compound lead chromate (PbCrO4) is an important solid
material that is used as a photosensitizer with a monoclinic
P21=n structure, which is usually called crocotite and is used as
a brilliant yellow pigment. Also, lead chromate is an important
photo-electricity solid functional material that has been widely
used in decorative systems, protective systems, and mass
coloration of fibers, plastics, papers, elastomers, and rubbers.

7
 CASE STUDY
◂ The lead chromate rods were prepared by adding
Pb2þ solution, at various concentrations and different
flow rates, to the chromate solution under vigorous
stirring and various temperatures. The reaction
between K2CrO4 and Pb(NO3)2 can be expressed as
follows:

8
◂ All samples were characterized by scanning
electron micrscopy (SEM) and energy-dispersive
x-ray analysis (EDAX, EDX, or EDS). Scanning
electron micrographs were recorded using on a
Philips XL30 series instrument using a gold film for
loading the dried particles on the instrument

9
 RESULTS
◂ Mixing solutions of anion and cation in order to
formation an insoluble inorgsnic salt such as lead
chromate is a commonly used technology for
synthesis many of water insoluble inorganic
materials. The control of particle size and shape is a
complex process requiring a fundamental
comprehensation of the interactions of reagents.
10
◂ The factors included in this study were lead
and chromate solution concentrations, flow
rate for addition of lead solution to the
chromate solution and the temperature of the
solution.

11
FIG. 1. EDAX spectrum of the synthesized lead
chromate nanorods by precipitation method.

12
FIG. 2. SEM images of rod-like lead chromate superstructures
obtained at different runs by precipitation method: (a) run 1, (b)
run 4, (c) run 5, and (d) run 9.

13
 CONCLUSION
◂ In summary, we have explored a simple, fast and
controllable method for the synthesis lead chromate
nanorods in aqueous media. Experimental conditions for
the synthesis ultrafine lead chromate particles using
precipitation method were optimized by Taguchi robust
design method with L9 orthogonal array.

14
THANK YOU

15
Journal of Dispersion Science and Technology, 33:254–257, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932691.2011.561173

Applying the Taguchi Robust Design to Optimization

of the Experimental Conditions for Synthesis of Lead
Chromate Nanorods
Seied Mahdi Pourmortazavi,1 Seiedeh Somayyeh Hajimirsadeghi,2 and
Mehdi Rahimi-Nasrabadi2
1
Faculty of Material and Manufacturing Technologies, Malek Ashtar University of Technology,
Tehran, Iran
2
Department of Chemistry, Islamic Azad University, Varamin Pishva Branch, Varamin, Iran

Orthogonal array design was employed as statistical method for controllable, simple, and fast
synthesis of highly uniform PbCrO4 nanorods by precipitation method. Lead chromate nanorods
were synthesized by addition of lead solution to chromate reagent. Effect of reaction conditions
on the width of lead chromate rods were quantitavely evaluated by analysis of variance. Finally,
optimum conditions for synthesis of lead chromate nanorods by this simple and fast method were
proposed. The results of analysis of variance showed that 0.001 mol/L lead and chromate ion con-
centrations are optimum conditions for producing lead chromate nanorods with 87
15 nm width.
Keywords Lead chromate, mixing, nanostructure, precipitation, statistical optimization

1. INTRODUCTION counterparts.[15–17] Therefore, the synthesis of lead chro-

The compound lead chromate (PbCrO4) is an important
solid material that is used as a photosensitizer with a
monoclinic P21=n structure, which is usually called croco-
tite and is used as a brilliant yellow pigment.[1,2] Also, lead
chromate is an important photo-electricity solid functional
material that has been widely used in decorative systems,
protective systems, and mass coloration of fibers, plastics,
papers, elastomers, and rubbers.[3–6] In addition, it has also
been used as a host material for photosensitizer, humidity
sensing resistor, etc.[7,8] Usually, PbCrO4 exists in two
kinds of crystal structures: the stable monoclinic structure
and the unstable orthorhombic structure.[4,9] Since the dis-
covery of carbon nanotubes in 1991,[10] one-dimensional
nanostructured materials (nanotubes, nanobelts, nano-
wires, and nanorods) have attracted considerable attention
from the scientific community due to their distinctive geo-
metries, novel physical and chemical properties, and poten-
tial applications in numerous areas such as nanoscale
electronics and photonics.[11–14] Recently, much effort has
been directed toward under standing the electronic, mag-
netic, and optical properties of these nanostructures
because these unique size- and shape-dependent properties
are physically or chemically different from their bulk
Received 12 November 2010; accepted 3 January 2011.
Address correspondence to Seiedeh Somayyeh Hajimirsadeghi,
P.O. Box 16765-3454, Tehran, Iran. E-mail: somayyehmirsadeghi@
yahoo.com
mate nanorods with well-controlled size and shape is of
great significance for its applications. To date, there have
been a few reports on the preparation of lead chromate
nanorods,[18–21] but few efforts were put to optimize experi-
mental conditions for synthesize uniformly ultra-long and
rectangular PbCrO4 nanorods. Herein, we develop a facile
precipitation method for the synthesis of rectangular
PbCrO4 nanorods without using any templates or addi-
tives. To the best of our knowledge, this is the first report
on the optimization of condition for synthesis of rectangu-
lar PbCrO4 nanorods with controllable width.
In this work, we focus on synthesis of lead chromate
ultrafine rods via a simple, fast and controlable precipi-
tation method. The particle size of lead chromate as a
rod-like inorganic particles is intrested because of its appli-
cations in eletronic industry and also in energetic material
formulations.[22]
Optimization is an important step for developing a syn-
thesis procedure for generation of nanoparticles. The
theory, methodology, and application of OAD as a chemo-
metric method for the optimization of the chemical pro-
cedure have been described in detail elsewhere.[23–30] The
aim of this study was to investigate the effect of some
experimental parameters on the diameter of lead chromate
rods and to find the best experimental conditions for syn-
thesis very fine rods of PbCrO4 by precipitation method.
Previous studies showed that reagent concentrations, tem-
perature and mixing flow rate have the main effects on

254
 PARAMETER OPTIMIZATION FOR SYNTHESIS LEAD CHROMATE NANORODS 255

the particle size of reaction products.[31] Therefore, an TABLE 2

experimental design proceduce was used to investigate the Results of the main effects for each variable on the
effects of four parameters on the diameter of formed lead diameter of PbCrO4 rods
chromate rods: concentration of lead ion solution, chro-
mate concentration, mixing flow rate, and temperature. Factor Level Result (nm)a

Lead ion concentration (mol=L) 0.01 115

2. EXPERIMENTAL Lead ion concentration (mol=L) 0.1 156
Lead ion concentration (mol=L) 1.0 203
Analytical-grade lead nitrate and potassium chromate
Chromate ion concentration (mol=L) 0.01 130
were used as received from Merck (Germany). The lead
Chromate ion concentration (mol=L) 0.1 196
chromate rods were prepared by adding Pb2þ solution, at
Chromate ion concentration (mol=L) 1.0 148
various concentrations and different flow rates, to the chro-
Flow rate of lead reagent (ml=min) 2.5 162
mate solution under vigorous stirring and various tempera-
Flow rate of lead reagent (ml=min) 10 156
tures. The reaction between K2CrO4 and Pb(NO3)2 can be
Flow rate of lead reagent (ml=min) 40 156
expressed as follows:
Temperaure ( C) 0 152
Temperaure ( C) 30 164
K2 CrO4 þPbðNO3 Þ2 ! PbCrO4 # þ2KNO3 :
Temperaure ( C) 60 158
a
After precipitation, the formed lead chromate was filtered These results are diameter of lead chromate micro and nano
and washed with distilled water three times. The product rods.
was then washed with ethanol and dried at 60 C for 2 hours.
To optimize experimental parameters for the synthesis 3. RESULTS AND DISCUSSION
lead chromate rods, an experimental design approach was Mixing solutions of anion and cation in order to forma-
followed. The variables (lead concentration, chromate con- tion an insoluble inorgsnic salt such as lead chromate is a
centration, flow rate of addition of lead reagent to the commonly used technology for synthesis many of water
chromate solution and temperature) were as shown in insoluble inorganic materials.[32] The control of particle size
Table 1. and shape is a complex process requiring a fundamental
All samples were characterized by scanning electron comprehensation of the interactions of reagents.[33] The pur-
micrscopy (SEM) and energy-dispersive x-ray analysis pose of this study was to determine how the various para-
(EDAX, EDX, or EDS). Scanning electron micrographs meters affect the diameter of lead chromate micro and
were recorded using on a Philips XL30 series instrument nanorods. The factors included in this study were lead and
using a gold film for loading the dried particles on the chromate solution concentrations, flow rate for addition of
instrument. lead solution to the chromate solution and the temperature
of the solution. Factors and levels tested are reported in
Table 1. Also, data obtained by results of the experiments
TABLE 1
Assignment of the factors and levels of the experiments
by using an OA9 (34) marix and mean width of
produced lead chromate
Diameter
Pb2þ CrO2
4 Pb2þ of
conc. conc. feed flow PbCrO4
Trial (mol= (mol= rate (ml= Temperature rods
number L) L) min) ( C) (nm)

1 0. 01 0.01 2.5 0 85
2 0. 01 0.1 10 30 157
3 0. 01 1.0 40 60 103
4 0.1 0.01 10 60 125
5 0.1 0.1 40 0 187
6 0.1 1.0 2.5 30 156
7 1.0 0.01 40 30 179
8 1.0 0.1 2.5 60 245
FIG. 1. EDAX spectrum of the synthesized lead chromate nanorods
9 1.0 1.0 10 0 185 by precipitation method.
256 S. M. POURMORTAZAVI ET AL.

ment of the experiment (Table 2). For example, to obtain

FIG. 2. SEM images of rod-like lead chromate superstructures
obtained at different runs by precipitation method: (a) run 1, (b) run 4,
(c) run 5, and (d) run 9.
are given in this table. Data obtained by performing
experiments of the factorial design were effects for each vari-
able. (Table 2 shows the results of these computations.)
The generated nanoparticles were characterized by
EDAX spectrum for the evaluation of their composition
and purity. Figure 1 shows the typical EDAX pattern of
the as-prepared PbCrO4 nanocrystallites. It is evident from
the peaks of Figure 1 that the product is highly pure and
they correspond to Pb and Cr with an average atomic per-
centage ratio of about 85.96:14.04. The elemental analysis
confirms the presence of corresponding elements in stochio-
metric percentage. Also, Figure 2 shows the SEM images for
three samples of lead chromate obtained by this method.
The analysis of data when there is no interaction
between variables, are including: 1) determine the optimum
condition, 2) identify the individual influence of each
factor, and 3) estimate the result at the optimum condition.
The analysis of variance (ANOVA) for the results (diam-
eter of lead chromate rods) are defined as shown in Table 3.
The mean values of the coefficients of variation of the
factors at each level were calculated according to assigin-
the mean value of lead chromate diameter for the effect
of the chromate solution concentration at level 1, the par-
ticle size of lead chromate rod of the nine trials in which
chromate was set at level 1 (triad 1, 4, and 7) were pooled
and divided by the number of values obtained (three
values). The mean value of the three levels of a factor
reveals how particle size of produced lead chromate rods
will change when the level of the factor is changed.
In this study, the effect of lead and chromate ion concen-
trations on the particle size of synthesized at three different
levels (0.01, 0.1, and 1.0 mol=L) was investigated. It was
found that concentration of lead ions is a significant para-
meter for the control diameter of lead chromate rods. Also,
our finding showed that concentration of chromate ions has
significant effect on the paticle size of lead chromate rods.
The effect of flow rate of lead reagent addition to the
reactor on the width of lead chromate rods was studied.
Three different flow rate (2.5, 10, and 40 ml=min) were
investigated. Our finding showed that flow rate is not a
significant parameter for paticle size control of product.
The effect of tempeature on the width of lead chromate
rods was studied. Three different temperature (0, 30, and
60 C) were investigated. The results of this study showed that
temperature has a significant effect on paticle size of product.
The ANOVA results of these experiments indicate that
(at 90% confidence level) except flow rate and temperature,
two other variables (lead and chromate ion concentrations)
have significant effects on the particle size of lead chromate
rods. In this work, the interactions between the varibles
were not considered. The results of ANOVA indicated that
enhancing concentration of lead solution from 0.01 to
1.0 mol=L increased the width of lead chromate rods. Also,
by increasing concentration of chromate from 0.01 to
0.1 mol=L, the width of lead chromate rods was increased.
However, by increasing concentration of chromate from
0.1 to 1.0 mol=L, the width of product rods was decreased.
Recall that for lead chromate rods with smaller diam-
eter, the study of the main factors shows that the optimum

TABLE 3
ANOVA table for synthesis lead chromate rods using precipitation procedure by OA9 (34) matrix with diameter of
synthesized lead chromate rods (nm) as the response
Pooleda

Factor Code DOF S V DOF S0 F0 P0

Lead concentration (mol=L) CPb 2 11634.0 5817.0 2 11634.0 83.9 60.4

Chromate concentration (mol=L) CCr 2 7116.7 3558.3 2 7116.7 51.3 36.7
Flow rate (ml=min) F 2 72.7 36.3 — — — —
Temperature ( C) T 2 204.7 102.3 — — — —
Error — — — — 4 277.3 — 2.9
a
The critical value was at 90% confidence level; pooled error results from pooling insignificant effect.
 PARAMETER OPTIMIZATION FOR SYNTHESIS LEAD CHROMATE NANORODS
conditions proposed acording to the results of ANOVA
are: 0.01 mol=L concentration of lead solution and
0.01 mol=L concentration of chromate solution. As a gen-
eral rule, the optimum performance (here, for synthesis
of lead chromate nanorods with smallest diameter) will
be calculated using the following expression:



T T T [8] Takabasi, K. and Toda, K. (1991) Sens. Mater., 2: 275–283.
Yopt ¼ þ Cx  þ Cy  ; [9] Knight, K.S. (2000) Miner. Mag., 64: 291–300.
N N N
where T=N is average diameter of lead chromate rods þ
contribution of Cx and Cy above average performance
and where, T is the grand total of all results, N is total
number of results, Yopt is diameter of nanorods at optimum
condition, and Cx and Cy are optimum concentrations of
lead and chromate solutions, respectively.
The procedure for calculation of the confidence interval
of the optimum diameter is discussed as follows. The CI
is given by:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Fa ðf1 ; f2 ÞVe
CI ¼
; [17] Jacobs, K., Zaziski, D., Scher, E.C., Herhold, A.B., and
ne
where Fa(f1, f2) is variance ratio for degree of freedom
(DOF) f1 and f2 at the level of significance a (in this work,
a ¼ 90%), and the confidence level is (1  a), f1 ¼ DOF of
mean (which always equals 1), f2 ¼ DOF of the error term,
ne ¼ number of equivalent replications, and given by
ne ¼ number of trials=DOF of mean (always 1) þ DOF of
all factors results used in the estimated. Statistical
calculations for determing the result and CI at optimum
condition showed that the width of lead chromate rods will
be 87
15 nm.
4. CONCLUSION
In summary, we have explored a simple, fast and con-
trollable method for the synthesis lead chromate nanorods
in aqueous media. Experimental conditions for the syn-
thesis ultrafine lead chromate particles using precipitation
method were optimized by Taguchi robust design method
with L9 orthogonal array. Some experimental parameters,
such as lead ion concentration and chromate ion concen-
tration were found to play significant roles in determining
particle size of lead chromate. The experiments proved that
by using this method, lead chromate nanorods could be
synthesized at optimum conditions.
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