Preparation of High Efficiency Lubricating Greases Using Iraqi Bentonite

Thickener Activated by Acid Treatment

Abstract
The rapid development in the engine industry requires greases with efficient properties that vary
depending on the severity of operating conditions and range from fluid to hard. Accordingly, this study
focused on preparing environmentally friendly inorganic lubricating greases that are not of soap origin in
their compositions and have properties suitable for working under different service conditions. To make
the manufacturing process economically feasible, emphasis was placed on using locally available raw
materials such as Iraqi clay as a solid porous thickener with both 60 and 150 Stoke base oils in addition
to hard and soft paraffin waxes all fabricated by Iraqi refineries. Raw bentonite has been treated with
various acids such as HCl, H₂SO₄, HNO₃, and a mixture of all acids for the purpose of activation and
converting the surface from hydrophilic to organophilic to facilitate dispersion in the organic base oil.
The physical properties of the treated clays (AIB) were studied using XRD, EDX, SEM, FTIR, and BET-
surface areas and pore volume analyses. The highest surface area of 221.051 m²/g and the highest
porosity of 0.5411 cm³/g were found by removing about 35 wt% aluminum from the bentonite lattice.
The crystal dimensions also increased, reaching a maximum range of 41.08 nm, while the degree of
crystallinity remained relatively high. It has been found that the type of acid used in treatment has a
striking effect on the structure and composition of the resulting thickeners, thus generating lubricating
greases with dissimilar properties. For that reason, synthetic greases have been observed to have a variety
of dropping points and working penetrations ranging between 86 ˚C with stock 60 and 300+ ˚C with
stock 150, as well as 202 with stock 150 and 427 with stock 60, respectively. The NLGI consistency
grades of the these greases ranged from semi-fluid using AIBMIX as a thickener with the base oil stock
60 and soft wax, to very firm using AIBHNO 3 as a thickener with the base oil stock 150 and hard wax.
Treatment with nitric acid resulted in an effective clay surface capable of absorbing both types of either
base oil stock and/or paraffinic wax in a homogeneous manner upon mixing compared to the rest of the
acid-treated bentonite thickener surfaces.

Keywords: Raw Iraqi Clay, Porous bentonite thickener, Base oil stock, Paraffin wax
additives, Acid treatment, Lubricating grease.

1. Introduction
Lubricating greases are a type of colloidal dispersion system and can be synthetic or mineral oil,
within a three-dimensional thickness network [1]. Grease is a common semi-solid lubricant
consisting of base oil, thickeners and optional improvers (i.e., additives). It is often used in roller
bearing systems when supply of oil is necessary and the lubricating oil must remain in a confined
chamber within engines [2]. Grease has been widely used to ensure the smooth functioning of
engines because it cannot flow away from contacting surfaces, giving it significant benefits over oil
in terms of load-carrying ability, corrosion resistance, and semi-permanent lubrication [3-4]. Despite
the fact that wear and friction between contacting surfaces is inevitable and is a major contributing
factor to mechanical failure, lubricating grease can reduce wear and friction on contacting surfaces
thus improving the mechanical durability of engines and extending their service life [5-7]. In fact, it
is the life of grease that determines how long mechanical components will last, and thus lubricating
grease is considered extremely important from an economic standpoint [8]. Currently, with the rapid
development of modern industry, there is an increasing demand for producing mechanical
equipment with high efficiency under harsh service conditions such as high load, speed and
temperature. Hence, the demand for lubricants used in these mechanical equipments is increasing
accordingly [9]. In general, there are several types of grease that are commonly used in industrial
production, such as lithium soap grease, calcium soap grease, sodium soap grease, aluminum soap
grease, barium soap grease, bentonite grease, polyurea grease, etc. [10]. Many methods are used to
prepare greases with better lubricity. Manufacturing new types of greases based on the use of
thickeners and additives, which are the two main technologies in the development taking place in
this field. In recent years, some new greases with excellent tribological specifications have been
successfully prepared, including complex greases such as calcium sulfonate, [11] tetraurea grease,
[12] polypropylene grease, [13] attapulgite grease, [14-15], and attapulgite-bentonite grease [16].
Here, attapulgite is a type of layered silicate material [17]. However, production cost remains one of
the most important factors that determine the production and industrial use of greases. In addition,
different types of solid additives have been used with thickeners in the production of lubricating oils
for the purpose of improving their operational properties. For example, various types of inorganic
powders, such as molybdenum disulfide [18-19], titanium dioxide [20], ferric oxide [21], silicon
dioxide [22-25], calcium carbonate [26-27], zinc oxide [28], lanthanum hydroxide [29], and
graphene [30]. They have been used with different types of bentonite plates to develop their
tribological properties [31]. It should be noted that typical thickeners consist of metallic soap that is
created by the saponification process of fatty substances. These materials include lithium, sodium,
aluminum and barium salts, which often cause direct and indirect environmental pollution [32, 33-
35]. Due to enhanced environmental awareness among the general public and implementation of
global legislation, there has been a continuous rise in the market demand for eco-friendly lubricants.
In contrast to traditional mineral soap thickeners, non-soapy products such as organic clay do not
contain any harmful metallic components, making them an environmentally friendly option as
thickeners [33, 35]. Moreover, the use of organic clays such as bentonite as a thickening agent in
lubricating grease formulations enhances their physical and chemical properties, leading to
exceptional performance in harsh operating conditions [36-38]. Greases are inherently unstable
materials that exhibit thixotropic behavior, which means that their characteristics may change over
time when exposed to shear forces. This depends on the complex microstructure of the thickeners
that are included in their composition, as they are subject to deterioration over long periods of use
[39-41]. From the above, choosing the thickener and oil from environmentally friendly, inexpensive
materials with high stability is considered an essential foundation for the success of commercially
manufactured greases. The use of non-metallic materials to manufacture lubricating greases has
attracted much attention. One example of this is bentonite grease, which is usually manufactured by
mixing base oil with surface-modified bentonite through pretreatment of the bentonite in various
ways, and this treatment has a significant impact on the effectiveness of the grease produced from it
[42]. Many clays are resistant to acid leaching, because much of the octahedral alumina layer is
sandwiched between two tetrahedral silica layers, and is not in direct contact with the aqueous acid
phase during treatment [43], making acid treatment of clays a major challenge. The negative charge
of the lattice is balanced by the exchangeable alkali metal cations, which are held on the basal
surface of the flakes as a surrounding cloud [44]. This is common in bentonite type thickener as
shown in Figure 1[45].
The aim of the current study is to produce different environmentally friendly inorganic
lubricating greases that do not contain soap origin and have various properties that make them
suitable for use in industrial applications for equipment operating under high and/or low stresses
according to their standard specifications. In order to reduce the cost of production, raw Iraqi
bentonite clays, which are available in large quantities, were used as a thickener after being treated
with various types of acids individually as well as with a mixture of these acids combined in equal
proportions. Two types of base oils produced in Iraqi refineries and two types of paraffin wax
produced locally were also employed. The aim is to compare acid treatment methods with each
other and verify the type of acid treatment that provides a porous bentonite surface with physical
properties that enable it to absorb base oil and paraffin wax in a homogeneous and highly efficient
manner to manufacture grease that has the highest consistency and highest hardness.
 Figure 1. Chemical composition of Bentonite [45]: Montmorillonite: (OH)12 A4 Si8 O16 . nH2O

2. The Experimental Work

2.1. Materials
The raw Iraqi bentonite (RIB) material used in this study was provided by the State Company for
Geological Survey and Exploration in Iraq, which consists of about 80% montmorillonite clay of
the Fe-Mg-Ca type with low swelling capacity. These clays were extracted from the western desert
of Iraq, which is about 40 km south of the H3 pumping station in the Tarifawi unit and the Safra
unit. These Iraqi clays are characterized by a relatively high cation exchange potential, with an
average ranging between 75-85%. Table 1 lists the chemical composition of RIB.
Table 1. Chemical composition of RIB raw Iraqi bentonite
Component SiO2 Al2O3 Fe2O3 K2O Na2O MgO CaO Cl *L.O.I SO3 P2O5 Impurities
Weight % 56.77 15.67 5.12 0.60 1.11 4.42 4.48 0.57 8.49 0.59 0.65 1.53
* L.O.I: Loss on ignition
Moreover, activated Iraqi bentonite (AIB) was prepared in the laboratory by chemically treating the
RIB with an acidic solution of HCl, H2SO4, and HNO3. Stock 60 and Stock 150 were used as base
oil, as well as soft and hard paraffin waxes as additives, all of which are local materials
manufactured by the Middle Refineries Company (MRC) / Al Doura Refineries in Iraq. It should be
noted that grease is a colloidal system and therefore sensitive to small amounts of surface active
substances. Thus, additives must be carefully selected in order to obtain the desired effect without
introducing unwanted side effects on other characteristics. In this study, a polar activator, methanol,
was also used. Table 2 shows the most important physical properties of the chemicals used in the
 current study, while Table 3 a and b show the properties of Iraqi base oil stocks and homemade
paraffin waxes.
Table 2. Chemical reagents and their commercial sources
Materials Hydrochloric acid Nitric acid Sulfuric acid Methanol DI Water
Composition HCl HNO3 H2SO4 CH3OH H2O
Density at 25 °C, g/mL 1.180 1.412 1.840 0.791 0.997
Purity % 37 69 98 99.8 99.99
Molecular weight, g/mol 36.46 63.01 98.08 32.04 18.02
Boiling point of the solution 110 122 290 64.7 99.97
at 1 atm, ˚C
Manufacture company LOBA CHEMIE. LOBA LOBA LOBA University of
CHEMIE. CHEMIE. CHEMIE. Technology
Origin India India India India Iraq, Baghdad

Table 3-a. Physical properties of Iraqi base oil stock

Physical property Base Oil Base Oil
Stock 60 Stock 150
Viscosity at 40 ˚C, c.St. 61.09 318.58
Viscosity at 100 ˚C, c.St. 8.05 25.12
*Viscosity index (V. I.) 95 Min. 93 Min.
**COC flash point, ˚C 220 Min. 260 Min.
Pour point, ˚C -6 Max. -3 Max.
***Color 1.5 3
Water content %vol. NiL NiL
* An index used to describe the viscosity-temperature behavior of lubricating oils.
** COC: Cleveland open cup method.
***The color of oil is measured by Lovibond apparatus according to ASTM D 1500 Color Scale.

Table 3-b. Physical properties of homemade paraffin wax

Physical property Soft wax Hard wax
Penetration at 25 ˚C 34 20
API gravity 37.3 34
Melting Point, ˚C 48 60 - 66
Oil content, wt.% 1.5 2
Color by ASTM D-1500 2.5 3

2.2. Characterization Techniques

X-ray diffraction (XRD) technique was used to analyze the structural composition of clay samples
through XRD patterns using a Panalytical X'PertPro diffractometer, UK. XRD measurements were
performed using a monochromatic copper Kα radiation source and a nickel filter with a
wavelength of 1.542 Å and the scan range of the measurements was 2θ = 0-80. Field emission
scanning electron microscopy (FESEM) was used to visualize surface morphologies using a
ZEISS FESEM analyzer from Germany at an accelerating voltage of 10 kV. FESEM
investigations were performed to determine the particle size and morphology of the bentonite
clays. Fourier transform infrared spectrophotometer (FTIR) technique was used to determine
structural functional groups, which was performed using a SHIMADZU S8400 FTIR
 spectrophotometer, Japan. Spectra were found within the wavelength range of 400 to 4000 cm.
Desorption-desorption data for N2 gas at 77 K were used to calculate specific surface areas and
total pore volumes. This analysis was performed using an automated gas absorption analyzer from
BEL, Japan, INC. It was based on Brunauer-Emmett-Teller (BET) techniques. Finally, the
chemical composition of the clays was evaluated using energy dispersive X-ray spectroscopy
(EDS) using OXFORD INSTRUMENT PLC, UK.

2.3. Preparation of activated Iraqi bentonite

Raw Iraqi bentonite clay (RIB) was dried at 100 °C for 4 h to get rid of moisture, and 20 g of dried
samples were taken for the purpose of activation using an acid solution consisting of each of the
following acids; HCl, H2SO4, and HNO3 separately, with a mixture of all acids at the same
concentration (i.e., 2 M) and in equal proportions for all types of solutions. In fact, each RIB
sample was mixed with 400 mL acid solution, and the resulting suspension was heated at 100 °C
under continuous stirring for 8 h. After acid treatment and obtaining the activated bentonite (AIB)
samples, each suspension is vacuum filtered and the precipitate is washed with deionized water
until its pH is approximately 7. The resulting cake is dried at 110 °C for 4 h. Finally, the powder
particles were obtained by mechanical grinding and sifting into smaller particles with a mesh size
of less than 75 μm to be stored in sealed plastic bottles. Table 4 shows the proposed nomenclature
for the bentonite clay samples and/or the greases prepared from them, while Figure 2 shows
photographs of the Iraqi bentonite clay samples used as thickeners in current study.

Table 4. Identification code for clay/grease samples

No. Code Code definition
1 RIB Raw Iraqi bentonite
2 AIBHNO3 Iraqi Bentonite activated using nitric acid
3 AIBH2SO4 Iraqi Bentonite activated using Sulfuric acid
4 AIBHCl Iraqi Bentonite activated using Hydrochloric acid
5 AIBMIX Iraqi Bentonite activated using a mixture of three acids; i.e., HCl, H 2SO4, and HNO3

Figure 2. Photographs of laboratory-treated types of Iraqi bentonite: A) AIBHNO 3, B) AIBHCl, C)

AIBH2SO4, D) AIBMIX, and E) RIB.
2.4. Preparation of Iraqi bentonite lubricating greases (IBLG)

Lubricating greases were manufactured using activated Iraqi bentonite as thickeners with the base
oil Stock 60 and Stock 150. Two types of waxes (i.e. soft and hard waxes) were also used as an
additive to avoid the separation that occurs between the thickener and the base oil as well as also to
increase the stability, solidity and consistency of the prepared grease. While methanol alcohol was
used as a polar activator that helps regulate the dispersion of the thickener in the base oil in a
homogeneous manner. Briefly, bentonite grease was prepared by placing the base oil in a stirred
vessel, and then an appropriate dispersing aid, represented by 1 wt% methanol, was added to the
base oil with continuous mixing at a speed of 2000 rpm for 30 minutes at a temperature of 40 ˚C to
produce a homogeneous mixture free of air bubbles. The AIB was ground in a three-roll mill for
three times and then slowly added to the base oil (i.e., 62% base oil and 27% thickener) inside the
vessel under vigorous stirring at 2000 rpm for 1 h. Subsequently, the wax was added to the
thickener-base oil mixture at a weight ratio of 10% with continuous mixing for 30 minutes to
improve the consistency of the produced grease. Finally, the resulting grease was left to cool slowly
to room temperature to obtain 16-types of homemade Iraqi greases, as shown in Figures 3 and 4.

Figure 3. Photographs of types of lubricating greases prepared using soft wax: A) AIBHCl- Base Oil Stock
60, B) AIBHCl-Base Oil Stock 150, C) AIBH 2SO4-Base Oil Stock 60, D) AIBH2SO4-Base Oil Stock 150, E)
AIBHNO3-Base Oil Stock 60, F) AIBHNO3-Base Oil Stock 150, G) AIBMIX-Base Oil Stock 60, and H)
AIBMIX- Base Oil Stock 150.

Figure 4. Photographs of types of lubricating greases prepared using hard wax: A) AIBHCl- Base Oil Stock
60, B) AIBHCl-Base Oil Stock 150, C) AIBH 2SO4-Base Oil Stock 60, D) AIBH2SO4-Base Oil Stock 150, E)
AIBHNO3-Base Oil Stock 60, F) AIBHNO3-Base Oil Stock 150, G) AIBMIX-Base Oil Stock 60, and H)
AIBMIX- Base Oil Stock 150.
3. Results and Discussion
3.1 Characterization of the bentonite clay
3.1.1 EDX analysis
Grease is basically lubricating oil thickened with a semi-solid or other stabilizing agent such as
soap or clay. Thickeners are of inorganic type, i.e. of non-soap origin, consisting mainly of
bentonite clay or montmorillonite, whose composition consists of hydrated aluminum silicate. They
are capable of absorbing large amounts of fluid and require waterproofing, and therefore it is
necessary to treat them, making them adequately resistant to water (i.e. converting them from
hydrophilic/lyophobic or organophobic) to non-hydrophilic/lyophilic or organophilic). Acid-
activated bentonite clay has physical and chemical properties that differ from non-activated clay.
Acid activation leads to modifying the surface area of bentonite and changing the proportions of its
structural components to a certain degree that depends on the type and the concentration of acid
used in the treatment. In fact, acid treatment mainly affects the removal of a percentage of the
aluminum layers to which the positive cation is attached to neutralize its charge within the
bentonite framework structure. Table 5 presents the changes in the chemical composition of
bentonite clay after acid treatment. A lower percentage of aluminum and associated magnesium and
calcium ions can clearly be observed within the composition of the acid-treated thickener samples,
No. 2-5, compared to the untreated bentonite thickener No.1, which is an inevitable consequence of
the de-alumination process. In fact, the H+ ion displaces metal ions, such as Ca2+ and Mg2+, within
the bentonite lattice, creating a clay with a highly reactive structure that helps the organic base oil
bind with protons to subsequently form grease.

Table 5. Results of EDX analysis of Iraqi bentonite clay before and after acid treatment
Samples Wt.% of Elements
No. Code Si O Al Ca Mg
1 RIB 46 30.2 14.2 5.1 4.5
2 AIBHCl 56.6 28.2 11.2 2.2 1.8
3 AIBH2SO4 57.8 34.2 5.1 1.9 1.0
4 AIBHNO3 55.7 34.9 6.1 2.1 1.2
5 AIBMIX 65.1 28.9 4.9 1.1 0.0

The elemental composition of bentonite was determined through EDX analysis in Figure 5. It
is noted that the clay consists mainly of silicon (Si) and aluminum (Al) elements, and that the
use of more severe treatment conditions using a mixture of three acids leads to the removal of
the largest amounts of aluminum and the formation of a more siliceous layer with large
crystals on the surface of the treated bentonite clay. It should be noted here that the
appearance of the gold element (Au) within the spectra of bentonite is the result of the ED-
Spectroscopy system, or also known as EDXR-Fluorescent, usually cannot work alone
without an SEM instrument. Indeed, the specimens must be electrically conductive, at least at
the surface, and electrically grounded to prevent the accumulation of electrostatic charge at
the surface. A nonconductive sample, such as bentonite, needs to be coated with a conductive
material before it is placed inside the bottom of the SEM column, since the excessive
charging from the electrons can damage the surface of the sample. Therefore, a sputter coater
onto the surface of the sample applies the conductive coating, such as gold or platinum with a
nanometer thickness [45]. Acid Activation treatment of clay generally leads to at least four
important changes in its structural framework [46]: (i) exchange of the hydrated interlayer
charge compensating cations for H + and their release into solution; (ii) delamination, or loss
of layer stacking of individual clay platelets into disoriented aggregates; (iii) dissolution of
the individual clay platelets and releasing the constituent cations into the solution; and (iv)

formation of a hydrous and highly porous phase.

Figure 5. EDX spectra of Iraqi bentonite: A) RIB, B) AIBHCl, C) AIBH 2SO4, D) AIBHNO3, and E)
AIBMIX.

3.1.2 XRD analysis

In Figure 6, the XRD patterns of raw clay (RIB) and acid-activated clays are shown over the
2θ range from 4 to 80°. It is noted that in all treated patterns the degree of crystallization is
almost high at the expense of the amorphous materials. In general, acid treatment causes a
striking change in the crystalline structure of clays. Since aluminum with associated cations
and other impurities between the clay layers are partially removed as a result of this
treatment, an increase in the intensity of the peaks reflected from the atoms within the clay
layers is sometimes an expected result.

Figure 6. Figure 3): XRD patterns of the smectite clay samples subjected to acid activation treatments: M)
Montmorillonite, P) Palygorskite, G) Gypsum, Q) Quartz, F) Feldspar, and C) Calcite.

Table 6 displays the fact that the XRD patterns of the untreated bentonite clays have
prominent major peaks that correspond to those of RIB clay. X-ray diffraction must occur for
any sample at a peak position corresponding to (2θ°) for the standard sample (RIB). The
percentage degree of crystallinity for the samples was calculated according to equation (1) by
dividing the sum of the main peak intensities for each treated sample by the sum of the main
peak intensities of the reference sample, which represent the basic components of Iraqi
bentonite such as montmorillonite, gypsum, quartz, etc [47-48].
 Degree of crystallinity=
∑ Peck intensities of the treated Iraqi bentonite clay ×% 100
∑ Peck intensities of thereference raw Iraqi bentonite clay
(1)

Furthermore, it is noted that there is a slight change in the value of 2θ° with the appearance of
distinct and strong peaks compared to the original clay in the XRD pattern of bentonite clays
activated with nitric acid, sulfuric acid, hydrochloric acid, and a mixture of these acids. This
observation in all types of treated specimens unambiguously confirms the crystalline nature
and also indicates the absence of partial collapse within their framework structure. It is
known that acid activation causes fundamental alterations within the structural components of
clays, as the structural units are affected due to the removal of part of the aluminum atoms
within the bentonite inter-layers, and there is always a shift in the XRD patterns to the right
(i.e. towards higher angles on the 2θ scale and the smallest diffraction d-spacing occurs
between parallel plans in the atomic lattice). This naturally leads to an increase in the average
dimension of the crystal size according to Scherrer’s law, while the full width of peak at half
maximum (FWHM) becomes narrower [49], and this may enhance the increase in the
percentage degree of crystallinity of the sample. The results obtained are consistent with the
results reached by previous studies in the aphid literature [46][50-52].

Table 6. Composition of the lattice spacing between the treated bentonite and raw Iraqi bentonite
Standard Raw Iraqi Treated Iraqi Bentonite Clay
Bentonite Clay
2θ (˚) RIB Clay 2θ (˚) AIBHNO3 2θ (˚) AIBH2SO4 2θ (˚) AIBHCl 2θ (˚) AIBMIX
intensity (I) intensity (I) intensity (I) intensity (I) intensity (I)

20.975 552 20.985 688 20.983 753 20.985 688 20.984 627
26.775 1554 26.796 2048 26.791 2205 26.795 1965 26.797 1735
50.225 181 50.242 212 50.245 275 50.245 215 50.246 250
60.075 131 60.095 167 60.085 201 60.082 184 60.093 178
68.375 129 68.385 161 68.377 179 68.392 173 68.381 173
Sum 2547 3276 3613 3225 2963
Degree of 100% 128.62% 141.85% 126.62% 116.33%
crystallinity

3.1.3 FESEM analysis

Raw Iraqi bentonite sample and treated bentonite samples were investigated using FESEM
analysis with 200 nm magnification. From the SEM images in Figure 7, it is clear that the
Iraqi bentonite sample identified as having the desired bentonite morphology with a
reasonably homogeneous structure and almost no obvious impurities and/or imperfections as
there is no obvious agglomeration into a large block. This observation is consistent with the
results of X-ray diffraction analysis, which demonstrated the absence of structural collapse of
the treated bentonite framework. This is the expected result when contaminants are removed
from the structure during careful acid leaching as clay layers appear visible with different
grain sizes sharing the same structure and this treatment often increases the distance between
the interlayers. The harsh acid leaching treatment conditions may lead to a clear effect on the
surface morphology. These results are somewhat agree with what has been reported in the
published literature [50][53].

Figure 7. SEM images of Iraqi bentonite: A) RIB, B) AIBHCl, C) AIBH 2SO4. D) AIBHNO3, and E)
AIBXIX.
In addition, bentonite crystals with sharp edges and large sizes on almost all sides were
developed in a random manner with average crystal sizes ranging from 21 nm for the RIB
sample to 41 nm for the AIBMIXED sample, as shown in Table 7. When comparing the
results in this table with the results in Table 5, it can be concluded that the lower the
percentage of aluminum within the structural framework of bentonite, the greater the average
crystal size of the sample, and this is completely consistent with the previously established
explanation in the interpretation of the XRD analysis results in Section 3.1.2.

Table 7. Average crystal sizes of raw and acid-treated Iraqi bentonite clays
Samples RIB AIBHCl AIBH₂SO₄ AIBHNO₃ AIBMIX
Average crystal 21.21 24.12 30.70 29.03 41.08
size (nm)

3.1.4FTIR analysis
In order to determine the impact of activated acid on active groups within Iraqi clays, FTIR
spectra spanning from 400 to 4000 cm-1 were investigated for both untreated raw clay and acid
activated bentonite samples. Figure 8 shows the FTIR spectra of these clays. The alterations in
the functional groups naturally reflect the modifications that occurred within the structural
framework throughout the acid activation treatment.

Figure 8. FTIR spectra of Iraqi bentonite before and after acid treatment

In fact, during acid activation of samples, protons from the acidic medium enter the clay
structures, attack the OH groups and change the adsorption bands attributed to the vibrations of
OH and octahedral cations. For example, it is noted that the stretching bands at 925, 1654, 3419,
and 3628 cm-1, which are related to the OH and Al-OH stretching, are clearly less intense for
some spectra after acid activation. Comparing with the spectrum of raw bentonite, a change in
the band corresponding to H-O-H stretching, which was detected at 998 cm -1, is observed with
increasing acid treatment. On the other hand, the tetrahedral transition occurred at 798 and 1091
cm-1, which is attributed to the Si-O-Si stretching peak that persisted obviously and accelerated
after acid activation. Likewise, the same observation is found for the characteristic peak of Si-O
extending at 470 cm-1. Most of the FTIR spectra values obtained were in stark agreement with
those reported in the published literature regarding clay activation with acids [50-53].

3.1.5BET-surface areas and pore volume analysis

Acid-activated bentonite clay displays superior physicochemical properties compared to its non-
activated equivalents. Surface area is one of the significant characteristics and acid activation
may modify the surface area and porous structure of bentonite to the necessary degree. It is
generally observed that the structure of raw clay expands through acid treatment, which leads to
increased porosity. Therefore, the surface area of modified bentonite is often larger than that of
natural, untreated bentonite. Table 8 displays the specific surface areas of clays that underwent
activation with different acids at 2 M concentrations. The data presented in the table indicate that
the clay samples exhibited a range of total surface areas from 26,538 m 2/g for the inactivated
natural clay to 221,051 m2/g for the clay activated with the mixture solution of the three acids.
As mentioned previously, the concentration and type of acid used in treatment fundamentally
affects the de-alumination process within the bentonite framework, and the increase in the
severity of the conditions used is accompanied by an increase in the openness of the clay
structure and an increase in porosity. Therefore, when comparing the results obtained with the
results previously presented in Table 5, it is noted that increasing the removal of aluminum
layers from the lattice of the bentonite sample leads to an increase in the surface area and an
increase in the pore volume for that sample. It is noted that the pore volume increased from
0.1812 cm³/g for raw bentonite to the highest value of 0.5411 cm³/g for clay activated with the
three acid mixtures. In fact, the presence of impurities in clays depends on the geological
composition of the original area in which they arise. Acid activation also removes impurities
between the layers of the structure. Accordingly, the goal in the treatment process is to enhance
structural integrity while removing ions and organic impurities that have become adsorbed
between the layers. Technically, opening the framework of the bentonite structure due to acid
treatment leads to the provision of a large pore space that nitrogen gas can enter to occupy in this
type of analysis. Hence, the results of the surface area and pore volume appear high for the
treated samples. The obtained textile property values were compared with those reported in the
available literature and a highly acceptable agreement was found [46][50][52-53]. What is more,
the treated clay has been shown to contain structurally large pores with a bigger crystallographic
distance (i.e., the average crystal size is relatively high, as previously described in Section 3.1.3).
Since additional pores can be generated and distributed over its surface as a natural result of acid
leaching. The increased pore size makes it easier for the base oil to enter the bentonite thickener
lattice during the grease preparation process.

Table 8. BET results for surface area and pore volume of Iraqi bentonite before and after acid treatment
Clay sample AIB AIBHCl AIBH2SO4 AIBHNO3 AIBMIXED
Specific surface area (m²/g) 26.538 63.375 213.031 195.783 221.051
Pore volume (cm³/g) 0.1812 0.2383 0.5063 0.4383 0.5411

3.2 Specifications of the activated Iraqi bentonite lubricating grease (AIBLG)

Different types of lubricating greases were prepared using treated bentonite thickeners mixed
with two types of base oil, and two types of paraffin wax were also added to improve the
stability and consistency of the produced grease. The laboratory-produced grease was subjected
to dropping point and grease penetration tests with up to 60 strokes at 25°C with a depth of 0.1
mm, and the appearance of NLGI consistency grades were also determined according to the
ASTM D217-02 method [54]. The NLGI consistency number, also called the NLGI grade, is a
measure of the relative hardness of the grease used for lubrication, and is used in the standard
classification of lubricants developed by the National Lubricating Grease Institute. The results of
the tests are listed in Tables 9 and 10. It is noted that there is a clear discrepancy in the
characteristics of the produced greases. In general, lubricating grease products using soft wax as
an additive ranged from semi-fluid to soft, while lubricating grease products using hard wax as
an additive ranged from normal to very firm. The lowest consistency of grease was not found,
which can be represented by fluid with an NLGI value of 000, nor was the highest consistency
of grease found among the products, which can be represented by hard with an NLGI value of 5.

Table 9. Test results for laboratory-prepared greases containing soft wax as an additive.
AIBLG sample Type of base oil Dropping point, ˚C Work penetration NLGI Grade Appearance
AIBHCl stock 60 93 408 00 Semi-Fluid
stock 150 127 362 0 Very Soft
AIBH2SO4 stock 60 115 393 00 Semi-Fluid
stock 150 153 347 0 Very Soft
AIBHNO3 stock 60 133 384 0 Very Soft
 stock 150 167 338 1 Soft
AIBMIX stock 60 86 427 00 Semi-Fluid
stock 150 147 353 0 Very Soft

AIBLG sample Type of base oil Dropping point ˚C Work penetration NLGI Grade Appearance

AIBHCl stock 60 167 267 2 Normal

stock 150 280 228 3 Firm
AIBH2SO4 stock 60 164 263 2 Normal
stock 150 266 212 3 Firm
AIBHNO3 stock 60 276 245 3 Firm
stock 150 300+ 202 4 Very Firm
AIBMIX stock 60 120 255 2 Normal
stock 150 215 233 3 Firm
Table 10. Test results for laboratory-prepared greases containing hard wax as an additive.

It should be noted that the usefulness of any type of grease product is determined by the purpose
for which it is used. For that reason, all types of greases produced are considered to have
economic and market benefits and can be used in various machines and engines according to
their need. In addition, Figures 9 and 10 show the effect of using soft and hard paraffin waxes on
the dropping point and work penetration of the produced greases. It was found that Iraqi
bentonite greases prepared using hard wax and base oil stock 150 have higher dropping points
and lower work penetration than their analogous greases prepared using soft wax and base oil
stock 60. This confirms that the use of hard wax and base oil stock 150 is practical in preparing
lubricating greases that have a harder consistency, which are used in engines operating at high
stresses, while on the contrary, the use of soft wax and base oil stock 60 can contribute to the
preparation lubricating greases that have a lower hardness consistency and greater elasticity,
which are usually utilized in equipment operating under low stress. Finally, it was concluded
that the Iraqi lubricating grease (AIBLG) with the highest consistency was prepared using
bentonite thickener activated by nitric acid with a base oil stock 150, using either soft or hard
wax as an additive. It can be said that treatment with nitric acid led to obtaining an Iraqi
bentonite thickener containing silicon (Si) and aluminum (Al) layers in ratios of 55.7 and 6.1,
respectively, with a specific surface area and pore volume of 195.783 m 2/g and 0.4383 cc/g,
respectively. This thickener with an average crystal size of 29.03 nm was seen to be more
efficient in creating a porous surface capable of absorbing both types of either base oil stock
and/or paraffinic wax in a homogeneous manner upon mixing compared to the rest of the acid-
treated bentonite thickener surfaces in the present study.

Base oil Stock 60 Base oil Stock 150

Figure 9. Dropping point and penetration of laboratory-produced grease using soft wax as an additive
Figure 10. Dropping point and penetration of laboratory-produced grease using hard wax as an additive

4. Conclusions
The current study focused on verifying the possibility of activating Iraqi bentonite using several
acids, namely hydrochloric, sulfuric, and nitric acids, as well as a mixture of these acids in equal
proportions. The acid treatment succeeded in producing the active bentonite thickener without
any collapse in the structural framework and with a relatively high degree of crystallization, with
an increase in the size of the crystals and surface area, as well as a striking increase in porosity
as a result of the removal of part of the aluminum layers from the clay lattice. The results
showed that the use of different types of acids fundamentally affects the treatment process, and
the largest removal of aluminum layers, associated ions, and other impurities was obtained using
a mixture of three acids. The highest surface area of 221.051 m²/g and the highest porosity of
0.5411 cm³/g were found by removing about 35 wt% of aluminum. The crystal dimensions also
increased to reach a maximum range of 41.08 nm. This was a result of the expansion of the
bentonite structure due to the acid leaching treatment. Lubricating greases with different
properties were successfully produced from all activated bentonite thickener surfaces by mixing
them with two types of light and heavy base oils (i.e., stock 60 and 150). It was found that the
use of two types of paraffin waxes (i.e., soft and hard) significantly affects the properties of the
produced grease. The study found that treating the bentonite surface with nitric acid yields a
porous thickener capable of absorbing both types of base oil stock and/or paraffinic wax in a
homogeneous manner with higher grease production efficiency compared to the rest of the acid
treatment. It was also found that environmentally friendly and low-cost inorganic greases have
different dropping points and work penetration ranging between 86 ˚C with stock 60 and 300+
˚C with stock 150, as well as 202 with stock 150 and 427 with stock 60, respectively. The
consistency of the produced greases ranged between semi-fluid using AIBMIX as a thickener
with the base oil stock 60 and soft wax, and very firm using AIBHNO 3 as a thickener with the
base oil stock 150 and hard wax.
Reference