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Production and

Characterization of WS2
Nano-Powders
Introduction

1.1 WS2

Tungsten (IV) sulphide (WS2) occurs naturally as tungstenite . It adopts a layered


structure. Because of this layered structure WS2 forms inorganic nanotubes, which were
discovered on an example of WS21.Bulk WS2 forms dark grey hexagonal crystals with a
layered structure and exhibits properties of a dry lubricant. When heated in oxygen
atmosphere it is converted toWO3 (Tungstic Oxide)., in absence of oxygen, it does not melt
but decomposes to tungsten and sulphur, at 1250 °C2.

WS2 can be produced by a number of methods involving oxides treatment with sulphide
and hydrosulphide sources. Other routes entail thermolysis of Tungsten Sulfides or the
equivalent.

Tungsten disulfide can also be used at higher pressure and temperature conditions, and
can resist from (-188oC) to (1316oC) in vacuum and (-270oC) to (650oC) in normal
atmosphere.

Structure of WS2
1.2 Properties

Bulk WS2 is a dark grey layered structured material exhibiting the properties of fry
lubricant. WS2 is a solid powder and is one of the most lubricious substances in the world. It
offers excellent dry lubricity with value of Coefficient of friction of 0.03, matchless to any
other substance including Graphite and Molybdenum Disulphide. Coated film can bear a load
to extremely high as 300,000psi. As this gives lowest Coefficient of Friction the applications
are unrestricted and could be tried with every feasible idea.

1.3 Applications

WS2 nanoparticles has good performance among solid lubricant materials also in high
temperature, pressure, vacuum, load, with radiation and corrosive media other than as a
general lubricant. Due to its low coefficient of friction, can be used as additives in the metal
powder for stable friction coefficient .Nanoscale WS2 has good resistance to oxidation and
can be used as additives to lubricating oil to effectively improve lubricancy, great pressure
and antiwear properties.WS2 nanoparticles are mainly used as oil catalysts.
Application of WS2
Typical applications include bearings, gears, valves, pump
components, injection moulding dies used in automotive and
aerospace applications.

Nano-structured WS2 is being studied profoundly for their potential applications, mostly
for storing Lithium and Hydrogen.3It is used to explore materials for electrochemical devices
and as material in lithium battery cathodes4, also used as catalyst in hydrogenation of CO2.

CO2+H2 CO+H2O

The need to replace the expensive and rare noble metal catalyst with earth-abundant
materials continues to be a strong driving force behind the current research in sustainable
energy technologies.5
Experimental procedure

2.1 Mixed Solvent method for synthesis of WS2:

For mixed solvent-method, required amount of commercial Tungsten disulfide


powder is added to two different solvents like water and ethanol, Toulene and ethanol etc.
The choice of the solvents depends on HSP (Hansen Solubility Parameter) and the volume
fraction of the solvent taken. Low HSP value for mixed solvents will give good results.

To calculate HSP parameter distance (Ra)

Ra = 4[(δD solute - δD solvent) 2 + (δp solute - δp solvent) 2 +

(δH solute – δH solvent) 2]0.5

δD δp δH for mixed solvents is

δDM = ᴓ1 δD1 + (1- ᴓ1) δD2 ----- a

δPM = ᴓ1 δP1 + (1- ᴓ1) δP2 ----- b

δHM = ᴓ1 δH1 + (1- ᴓ1) δH2 ----- c

Where 1 and 2 are the two different mixed and ᴓ1 is the volume fraction of the first solvent.
By substituting the above values in the main equation we can get the value of Ra.

For synthesis of WS2 using the above method, commercial powder has been added to
Ethanol/water and Toulene/water combinations in 30% volume fraction of Ethanol and
Toulene. The contents are added to a flask and are sonicated for 8hours continuously. The
sonicated content should be centrifuged for 20min at 3500rpm .Later the centrifuged product
is being collected and kept for drying.
For 30% volume fraction of Ethanol/water Ra value is

 Weight of WS2 taken is 360mg


 Volume of Ethanol is 42ml
 Volume of Water is 78ml

For 30% volume fraction of Toulene/water:

 Weight of WS2 taken is 360mg


 Volume of Toulene is 42ml
 Volume of Water is 78ml

Commercial WS2 + Ethanol/Water or


Toulene/water

Sonicated for 8hrs

Centrifuged at 3500rpm for 2hrs

Centrifuged sample is collected and dried

Flow chart for synthesis of WS2 using mixed solvent method


2.2 Heat Treatment for WS2 synthesis using tubular furnace:

2.2.1 Preparation of Precursor

Prior to experiment Thiourea and Tungstic acid are pot blended in 1:48 ratio, by
adding the powders in a container with 5:1 ball to powder ratio.

H2WO4+ 2CH4 WS2 + 2CH4 N2O + H2O2

Precursor information

Precursor name Weight taken( gms)

Tungstic acid 1gm

Thiourea 48gms

2.2.2 Synthesis of WS2 from precursor

The blended powder is taken in small quantity in alumina crucible and heat treated
in tubular furnace under N2 atmosphere at 773K for 3hrs at 3oC per min heating rate. After
3hrs of heating the sample was cooled to room temperature under N2 atmosphere and a black
powder is obtained (WS2).

2.3 Hydrothermal synthesis of WS2:

2.3.1 Precursor preparation

In this synthesis route the precursor is prepared by a mechanical activated method, i.e
ball-milling of commercial powder by a solvent. Before starting the ball-mill should be
subjected to blank run with Toulene at 250rpm for about 24 to 48 hrs to remove any traces of
impurities.

After cleaning Tungsten Oxide (WO3) powder with Toulene should be added to each
vial .The volume of Toulene should be as such that WO3 gets completely immersed in
solvent. The milling is continuously done for 48hrs at 250rpm for a 15min pause time for
each hour. Then the milled powder is collected dried, grounded and stored.

Ball to Powder ratio for ball-milling is 5:1. Each ball in the vial is 7gms.

For 1gm of WO3 5gms of ball should be added (Each ball weights about
7gms)

X gms of WO3 7gms of ball

So 1.4gms of WO3 should be added for each ball. For 49 balls 68.6gms of WO3 should
be used with 50ml of Toulene in each vial.

Once the WO3 is ready, it is pot-blended with Sulphur with 3:1 (Sulphur to WO3) ratio
using steel balls with ball to powder ratio of 5:1 for 24hrs.

Amount of sulphur added to blend with 30gms of WO3

For 1gm of WO3 3gms of sulphur is added

For 30 gms of WO3 60gms of sulphur added

2.3.2 Synthesis of WS2 from the precursor

This (WO3+S) blended powder is heat treated at high temperature and pressure in a
furnace at a temperature 610oC initially under a positive pressure H2 atmosphere, at
1.75Kg/cm2 for 2hrs at a rate of 3oC per min. Once the furnace starts reaching the required
temperature the pressure will be increased to 2Kg/Cm2. Then the powder is cooled under
same pressure and the gas is released slowly to obtain the black product WS2.
2.4 Synthesis of WO3:

2.4.1: Synthesis of WO3 with the presence of carbon

Commercial WO3 was synthesized using a hydrothermal methodology, with an


initial ball-milled of WO3 with Toulene to incorporate carbon from toulene into WO3. The
milling process should continuously for 60hrs.Then the precursor is heat treated at different
temperatures ranging from 300oC to 600oC under vacuum, when the pressure reaches
0.03mbar, at 3oC per min rate.

Another set of samples are heat treated from 300oC to 600oC under positive pressure,
Argon in this synthesis at 3oC rise in temperature per min. First we should fill Ar till the
pressure reaches 1.75Kg/Cm2 and then should start heating. Later when the temperature of
the furnace reaches maximum the pressure in the gauge reaches 2 Kg/Cm2. The furnace
should be cooled in Ar atmosphere. At different conditions we get different coloured final
product.

2.4.1: Synthesis of WO3 after removing of carbon

60hrs ball-milled WO3 with toulene is heated at 350oC at 3oC rise per minute for
2hrs to remove carbon content. The precursor was subjected to heat treatment at a higher
temperature 610oC under Hydrogen atmosphere at a rate of 3oC per min for 2hrs.

2.5 Coatings of commercial and synthesized powders on SS coupons

Commercial WS2 of different grades and hydrothermally synthesized WS2 are


coated as a thin layer on polished stainless steel substrate (SS) by just smudging or rubbing
trace amount of the powder on to the substrate to make the powder stick onto it. Then these
coated coupons are characterized for Coefficient of friction (COF).

Another set of coatings are made by mixing required quantity of Fe36%Ni ,


Fe36%Ni + 10%WS2 and Fe36%Ni + 20%WS2 with few drops of 8% Polyvinyl alcohol
(PVA) to make a fine paste. This paste was applied as a thin coat on to the steel substrates
using a spatula. The coupons are dried and then laser processed for the powder to stick onto
the substrate. Later these coatings are tested for COF.

Conditions used for laser processing

Pulse Width 3ms

Pulse energy 3J

Repetition rate 40Hz

Processing speed 10mm/s

Line to Line distance 0.4mm

Spot diameter 0.6mm

Assisted gas Argon gas

Pressure of gas 2bar


Results and Discussion

4.1 Structural Properties:

4.1.1 Structural Properties of Commercial WS2 and synthesized WS2

The structural properties of commercial and WS2 powder synthesized by different


routes and synthesized WO3 are studied using X-ray diffraction studies. Figure
shows the XRD pattern of WS2.For WS2 and WO3 all the peaks are assigned to WS2 and
WO3.These XRD patterns are can be compared using JCPDS cards. As can be clearly seen
from the spectra, the peak intensities of the ( ) plane is high compared to other peaks for
WS2 and ( ) peak for WO3 .There is no impurity peak observed in any of the spectra.

XRD pattern of WS2 synthesized by mixed solvent method


(Ethanol and Water)
XRD pattern of WS2 synthesized by mixed solvent method
(Toulene and Water)

XRD pattern of WS2 synthesized by hydrothermal method


4.1.2 Structural Properties of synthesized WO3 under Argon and Vacuum from
3000C to 6000C
4.1.2.1Under Argon

XRD pattern of WO3 synthesized at 3000C under Ar


XRD pattern of WO3 synthesized at 4000C under Ar

XRD pattern of WO3 synthesized at 5000C under Ar


XRD pattern of WO3 synthesized at 5000C under Ar

4.1.2.2 under Vacuum

XRD pattern of WO3 synthesized at 3000C under vacuum


XRD pattern of WO3 synthesized at 4000C under vacuum

XRD pattern of WO3 synthesized at 5000C under vacuum


XRD pattern of WO3 synthesized at 5000C under vacuum

4.4 Morphological properties:

To study the morphology FE-SEM studies are carried out which reveals the nanostructures of
WS2 and WO3.Formation of different nanostructures can be controlled by different synthesis routes
and also on the temperature of heat treatment.
4.4.1 Morphological properties of Commercial and synthesized Ws 2

FE-SEM of Ethanol/Water, Toulene/Water and heat treated WS2

FE-SEM of Fe-Ni, Fe-Ni+ heat treated Ws2 and heat treated WS2 coated on SS substrate
References

1
Tenne R, Margulis L, Genut M, Hodes G (1992). "Polyhedral and cylindrical
structures of tungsten disulphide". Nature 360 (6403): 444–446.

2
Mary Eagleson (1994). Concise encyclopedia Chemistry. Walter de Gruyter.
P.1129. ISBN 978-3-11-011451-5.

3
http://pubs.acs.org/doi/full/10.1021/jz300480w

4
Erik Lassner, Wolf-Dieter Schubert (1999). Tungsten: properties, chemistry,
technology of the element, alloys, and chemical compounds. Springer. pp. 374–
. ISBN 978-0-306-45053-2.Retrieved 6 November 2011.

5
Highly active hydrogen evolution catalysis from metallic WS2 nanosheets
Mark A. Lukowski, Andrew S. Daniel, Caroline R. English, Fei Meng, Audrey
Forticaux, Robert J. Hamers and Song Jin* Cite this: Energy Environ. Sci.,
2014, 7, 2608 Received 29th April 2014 and Accepted 21st May 2014