Powder Technology 162 (2006) 83 – 86

www.elsevier.com/locate/powtec

Preparation and characterization of monoclinic sulfur nanoparticles

by water-in-oil microemulsions technique
Yiming Guo, Jingzhe Zhao, Shaofeng Yang, Kaifeng Yu, Zichen Wang *, Hengbin Zhang
College of Chemistry, Jilin University, No. 2519 JieFang Road, ChangChun 130023, PR China

Received 4 September 2004; received in revised form 7 June 2005

Available online 30 January 2006

Abstract

Nanosized monoclinic sulfur particles have been successfully prepared via the chemical reaction between sodium polysulfide and hydrochloric
acid in a reverse microemulsions system, with theolin, butanol, and a mixture of Span80 and Tween80 (weight ratio 8 : 1) as the oil phase, co-
surfactant and surfactant, respectively. Transparent microemulsions were obtained by mixing the oil phase, surfactant, co-surfactant, and the
aqueous phase in appropriate proportion using an emulsification machine at the room temperature. The resulting sulfur nanoparticles were
characterized by dynamic light scattering (DLS), X-ray diffraction (XRD), infrared spectroscopy (IR) and transmission electron microscopy
(TEM).
D 2005 Elsevier B.V. All rights reserved.

Keywords: Reverse microemulsions; Sulfur; Nanoparticles

1. Introduction acid, chemistry fiber, chemical fertilizer, and rubber, pharma-

ceutical industry, and bioleaching processes etc. [15]. The size
The preparation and characterization of nanoparticles have of sulfur particles is an important factor affecting their
attracted considerable interest for their peculiar quantum-size properties and utilizations. Chemistry vapor deposition
properties and high specific surface areas [1 – 4]. Some (CVD) is a primary method for the preparation of sulfur
methods have been developed to control the size of nanopar- particulate in the past [16]. By using template-free technology
ticles, for instance, vesicles [5], Langmuir– Blodgett films [6], etc., sulfur microtubules and sulfur films were prepared
surface-active supports [7], and reverse microemulsions [8] etc. successfully [17 18]. In the present work, we describe the
Microemulsions have been intensively used as spatially preparation of nanosized sulfur particles in reverse microemul-
constrained micro-reactors to control the growth of inorganic sion systems. The W/O microemulsions, used in the prepara-
materials and is drawing more and more attention [9– 11]. tion, consist of the following components: butanol, a mixture
Water-in-oil (W/O) microemulsions are isotropic and thermo- of Span80 and Tween80, theolin, and water solutions of both
dynamically stable mixtures consisting of nanosized aqueous sodium polysulfide and hydrochloric acid (HCl).
droplets, which are surrounded by a monolayer of surfactant
molecules dispersed in a continuous non-polar organic 2. Experimental
medium. Microemulsion system thus can provide a proper
microenvironment for the formation of non-aggregated nano- 2.1. Materials
particles [12 –14]. Therefore, microemulsion approach is a
promising method for the preparation of nanosized particles. Sulfur powder (20 –50 Am) was sublimed sulfur. Sodium
Sulfur is a chemically and biologically active element, and sulfide, Span80, Tween80, theolin, butanol, hydrochloric acid
is widely used in many fields, such as the production of sulfuric and acetone were of reagent grade. The water used throughout
this work was the distiller water. Hitachi-8100IV transmission
electron microscope (TEM), Siemens D5005 X-ray diffrac-
* Corresponding author. Tel./fax: +86 431 8499134. tometer (XRD), Ominic system 2000 infrared spectroscope
E-mail address: [email protected] (Z. Wang). (IR), and MALVERN Zeta-size 3000HSA analyzer.
0032-5910/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2005.12.012
84 Y. Guo et al. / Powder Technology 162 (2006) 83 – 86

Table 1 graphite monochromatized CuKa radiation (k = 1.5418 Å),

Compositions of microemulsion systems employing a scanning rate of 0.05-/s in the 20 range from
Microemulsions I Microemulsions II 10- to 70-. Particle distribution was obtained by dynamic light
Aqueous phase 2 mol/L Na2Sx : 25 ml 4 mol/L HCl : 25 ml scattering (DLS) using MALVERN Zeta-size 3000HSA
Surfactant S and T: 60 g S and T: 60 g analyzer. The size and shape of particles were observed under
Co-surfactant Butanol : 10 ml Butanol : 10 ml
a Hitachi-8100IV transmission electron microscope (TEM) at
Oil phase Theolin : 450 ml Theolin : 450 ml
100 kV. The samples for TEM measurement were prepared by
deposition of an ultrasonically dispersed suspension of the
2.2. Particles synthesis sulfur product in ethyl alcohol on a carbon-coated copper grid.
Infrared (IR) spectra were recorded by Ominic system 2000
2.2.1. Preparation of sodium polysulfide solution Infrared spectroscope employing a potassium bromide (KBr)
Stock sulfur powder was ground fully in a mortar to form pellet method.
particles of about 5 Am. 12.8 g of grounded sulfur powder
was added into a flask that has been filled with 100 ml of 3. Results and discussion
sodium sulfide solution (2 mol/L). The reaction was
performed at room temperature for 30 min under stirring. 3.1. Preparation of microemulsions system
The color of the solution changed slowly to orange-yellow
with the dissolving of sulfur and sodium polysulfide (Na2Sx ) The studied microemulsions are based on five components:
solution was obtained. theolin, Span80, Tween80, butanol and water. Clear or turbid
ðx  1ÞS þ Na2 S ! Na2 Sx microemulsions of sodium polysulfide and hydrochloric acid
have been obtained depending on the relative quantities of the
2.2.2. Preparation of microemulsions components. The use of clear and turbid microemulsions led
In order to prepare reverse microemulsions, theolin, a to different sizes of the resulting sulfur particles. For clear
mixture of Span80 and Tween80 (S&T), butanol and water microemulsions, the ratio of theolin : S&T: butanol : water is
was used as oil phase, surfactant, co-surfactant and aqueous 90 : 12 : 2 : 5 (ml/g/ml/ml). Aqueous phase of sodium polysul-
phase, respectively. The two compositions of the surfactant fide solution and hydrochloric acid solution are contained in
had a fixed weight ratio (Span80 : Tween80 = 8 : 1). A typical microemulsions I and II, respectively. Micro-droplets contain-
preparation of clear microemulsions of sodium polysulfide ing aqueous phase in both microemulsion systems can be
(microemulsion I) and hydrochloric acid (microemulsion II) regarded as nanoreactors, in which sodium polysulfide or
were described below. 60 g of S&T and 10 ml of butanol hydrochloric acid are soluble and steady. When the above two
were added into 450 ml of theolin under stirring to form an kinds of reactors collide with each other, a certain reaction
organic mixture. Just after this organic mixture was well occurs and sulfur nanoparticles can form. Table 1 shows the
distributed, 25 ml of sodium polysulfide solution or compositions of the microemulsions.
hydrochloric acid solution was added in it at room
temperature. Then transparent reverse microemulsion I or II
were obtained by agitating the mixture using an emulsifica- Size distribution(s)
tion machine.

2.2.3. Synthesis of sulfur nanoparticles a b

An appropriate amounts of microemulsion I and II were
40
mixed together, leading to the formation of insoluble sulfur
particles. After reaction, acetone was added to break the steady
% in class

microemulsion system and cause the sedimentation of the

synthesized sulfur particles. The precipitate was separated by
centrifugation at 4000 r/min for 15 min. Then it was repeatedly
washed with acetone and distilled water to remove oil, surfactant
and co-surfactant. Finally, the precipitate was dried in vacuum at 20
80 for 2 h. The product was light yellow powder. The following
chemical reaction occurred in the droplets of the microemulsions
when microemulsions I and II were mixed together:
Na2 Sx þ 2 HCl ! 2 NaCl þ H2 S þ ðx  1ÞS

2.3. Characterization 5 10 50 100 5001000

Diameter (nm)
The product was characterized by X-ray diffraction (XRD) Fig. 1. Size distribution of the sulfur nanoparticles (a) Sodium polysulfide as
using Siemens D5005 X-ray diffractometer equipped with inorganic reactant, and (b) Ammonium polysulfide as inorganic reactant.
 Y. Guo et al. / Powder Technology 162 (2006) 83 – 86 85

1000
b

23.08

800
b
Intensity (a.u.)

600

T%
27.7
400 25.84 a

31.4
200 15.4 37.04 42.78

0 25.4 29.72
4000 3600 3200 2800 2400 2000 1600 1200 800 400
10 20 30 40 50 60 70 (cm-1)
2θ (o)
Fig. 4. IR spectra of sulfur. (a) high purity monoclinic sulfur; (b) the resulting
Fig. 2. XRD pattern of the sulfur nanoparticles. sulfur nanoparticles.

3.2. Effect of inorganic reactant values for monoclinic phase sulfur (JCPDS N34-0941). The
average crystallite size of the as-prepared sulfur particles is
Alkali metal sulfides and ammonium sulfide can dissolve about 20 nm, according to the Debye – Scherrer formula
in water easily. Sulfur can be dissolved in the solution of (D = 0.9k / b cosh).
alkali metal sulfides or ammonium sulfide to form polysul-
fide. The species of inorganic reactant used in the aqueous 3.4. Analysis of transmission electron microscope (TEM)
phase had a significant effect on the size of the resulting
sulfur particles. Fig. 1 shows the size distribution of the sulfur Fig. 3 shows the TEM image of the product, indicating that
particles obtained by DLS. The sulfur particles prepared from the sulfur particles are well-arranged spheres, having a mean
both sodium polysulfide (25 ml, 2 mol/L) and ammonium size of 20 nm. Since the chemical reaction of sodium
polysulfide (25 ml, 2 mol/L) is in nanometer size, with a polysulfide and hydrochloric acid were restricted in the water
narrow size distribution, but they have different average droplets of microemulsions, the agglomeration of sulfur crystal
particle size. The average diameter of sulfur nanoparticles in microemulsions was avoided during preparation, and the
with sodium polysulfide as the reactant is about 20 nm, while size of the sulfur particles was only influenced by the diameter
the one with ammonium polysulfide as the reactant is about of the water droplets. Therefore, the size of the resulting sulfur
35 nm. nanoparticles was regulated.
On the other hand, the average diameter of sulfur particles
prepared from 0.5 and 2 mol/L sodium polysulfide solutions is 3.5. Analysis of infrared spectroscope (IR)
similar to each other. Therefore, it is concluded that the
concentration of the sodium polysulfide has no significant Fig. 4 shows the IR spectrum of the product (curve b). It
effect on the size of the resulting sulfur particles in a can be found that every sulfur character peak of monoclinic
determinate concentration range. sulfur is present in the IR spectra of the product and the
shapes of the peaks are identical with those of the monoclinic
3.3. Analysis of X-ray diffraction (XRD) sulfur (high purity, Merck; curve a). The two curves are
parallel, implying that new chemistry linkage does not form
Fig. 2 shows that the XRD pattern of the as-prepared sulfur on the sulfur nanoparticles. All these indicate that the
nanoparticles had broad peaks. The positions and intensities of composition of the sulfur nanoparticles consists of sulfur
the diffraction peaks are in good agreement with the literature element only.

Fig. 3. TEM image of the sulfur nanoparticles.

86 Y. Guo et al. / Powder Technology 162 (2006) 83 – 86

4. Conclusions References

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