Chemistry and Technology of Fuels and Oils, Vol. 50, No. 2, May, 2014 (Russian Original No.

2, March – April, 2014)

STUDY OF STRUCTURAL-MECHANICAL PROPERTIES OF PARAFFIN-CONTAINING

PETROLEUM PRODUCTS

A. S. Abubakarova,1 Zh. T. Khadisova,1 E. A. Aleksandrova,2 and B. E. Krasavtsev3

A new design of a laboratory installation for determining the strength P m , plasticity Pl, and
contraction DV of solid paraffin-containing petroleum products with automatic recording of
measurement results is described. A comparative analysis is made of P m, Pl, and DV of solid crude
oil paraffins, ceresines, and waxes at 25°C. The mechanisms of formation of disperse structures of
commercial paraffin-containing petroleum products and dominant role of n-alkanes in their
composition as strength carriers are ascertained. Strain-hardening of the disperse structure of
commercial ceresine and wax specimens containing 40-60% hydrocarbons that do not form a complex
with carbamide is observed for the first time.
Key words: paraffin, ceresine, wax, strength, plasticity, volume shrinkage, strain-hardening.

Solid petroleum paraffins, ceresines, waxes, and compositions made from these materials are essential
to the growth of more than 30 sectors of industry, including electronics, machine construction, packaging,
wood technology, and the food industry. Among the keys to the production and use of paraffin-bearing
petroleum products are processes which involve the formation of a solid phase and the subsequent formation
of a dispersed three-dimensional structure. The future development of new paraffin-ceresine-wax compositions
with prescribed properties should be based on an understanding of the features of the structure-forming
process in these materials, methods that might be used to control this process, and changes in the properties
of the structures that are formed.
The goal of the investigation being discussed in this article is to comparatively evaluate the
structural-mechanical properties of paraffins, ceresines, and waxes in order to provide scientific validation for
their subsequent compounding and the production of alloys with prescribed properties.

____________________________________________________________________________________________________
1
Groznensk State University of Petroleum Engineering. 2Kuban State Agrarian University, Krasnodar,
Russia. 3 OOO Yuzhnyi Polyus, Kropotkin, Russia; E-mail: janna_h@list.ru. Translated from Khimiya i
Tekhnologiya Topliv i Masel, No. 2, pp. 38 – 41, March – April, 2014.

0009-3092/14/5002–0149 2014 Springer Science+Business Media New York 149

 Studies were conducted on specially developed unit “Mikro-02M,” which has its own automatic
control system (ACS). Figure 1 presents a diagram of the unit. The “Mikro-02M” unit consists of a
structure-forming cuvette I, a program-based system for changing temperature II, and equipment III to measure
the limiting shear stress. The limiting shear stress is used to evaluate the strength of the structure which is
formed in the test specimen. The cuvette, designed to form paraffin dispersions with a flaw-free structure,
combines the features of a dilatometer with the characteristics of an improved Weiler-Rebinder
instrument [1, 2] for low-strength structures. This instrument is a measurement cell 1 with a volume
of 5·10 -7 m 3. The cylindrical inside surface 2 of the large part of the cell is fluted. The top part of the cell has
a sealing cap 3 with a temperature sensor, while the lower part contains a self-sealing piston 4. The lower part
of the cell (20% of its length) has a smooth surface to allow the piston to move freely. The piston is mechanically
coupled to a pneumatic membrane actuator (MPA) 5, which acts together with pneumatic device 6 to create a
force that compresses the specimen. Thus, the piston determines the change in the volume V of the test
system. The linear displacement of the piston - which is proportional to the change in V - is recorded by
mechano-pneumatic converter 7 with the aid of recording unit 8.
The limiting shear stress Pm of the structured specimen is measured after the sealing
cap 3 has been removed. The measurement is performed by using a system designed for programmed loading
of the piston 5 to create a mechanical load F that forces the body of the specimen out of the cell (the
method dP/d = const). The minimum force F m which corresponds to fracture of the specimen on the cylindrical
surface that is bonded to the cell characterizes the strength of the specimen P m.
The method used to study the strength of paraffin-bearing petroleum products consists of the following.
The measurement cell is heated to a specified temperature. The delivery of compressed air into the top
chamber of the MPA moves the piston to its lowest position. The top part of the cell is sealed with the
cap after the specimen has been loaded (in the solid or liquid state) and heated to the prescribed
temperature T h. Air pressure is then relieved in the top chamber of the MPA and a pneumatic reducer is used
to create a small amount of excess pressure in the actuator’s bottom chamber. This ensures that there is no air
left in the cell. After the cell has been correctly filled with the product, the latter is cooled to a prescribed

Heat carrier

Coolant

Fig. 1. Diagram of a unit for studying thermal and structural-mechanical properties

(the notation is explained in the text).

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temperature in accordance with the program. Air pressure is relieved in the MPA chamber and the sealing cap
is removed. To determine the strength of the specimen P m , its contraction (volume shrinkage) V, and its
plasticity Pl, air pressure is raised at a constant rate (dP/d = const) in the bottom chamber of the MPA by
means of a programmed device and the “stress P – strain ” curve is recorded by recording units (Fig. 2).
The limiting shear stress P m (N/m 2), characterizing the strength of the structures, was calculated from
the formula:

Pm  Fm / S

where F m is the minimum force applied to the specimen for its fracture, N; S is the surface area of the side of
the body of the specimen at the test temperature, m 2; S = dl T ; d is the inside diameter of the measurement
cell, m; l T is the length of the body of the specimen undergoing fracture at the test temperature T, m.
Since the load F m is created by a membrane actuator that acts in one direction. it can be determined
from the formulas:

Fm  Pa Feff

 
Feff   D 2  DD1  D12 / 2

where P a is the lowest compressed-air pressure in the bottom chamber of the MPA that results in fracture of
the specimen, Pa; F ef is the effective area of the MPA membrane with the rigid center, m2 ; D is the diameter of
the membrane, m; D 1 = 0.8D is the diameter of the membrane with the rigid center, m.
The values of D and D 1 are constant for an MPA of the given design, so that F m is always proportional
to P a . The error of measurement of the limiting shear stress is no greater than 3%.
All of the above-described operations performed in preparing the instruments and filling the cell were
also performed when we determined the value of V of the specimens as the temperature of their melts
decreased. The piston ascends as each specimen contracts during its cooling. The piston’s upward
motion is recorded by a recording unit. The following formula was used to calculate the amount of
contraction V (in %) at any temperature:

Fig. 2. Types of “stress – strain” (P – ) curves.

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 V2  V1
ΔV  100
V2
or

l 2  l1
ΔV  100
l2

where V 1 and V 2 are the volumes of the specimen at the respective temperatures T 1 and T 2, m 2; l 1 and l 2 are the
lengths of the body of the specimen at temperatures T 1 and T 2, m.
With allowance for the accuracy rating of the transducers and recording devices that were used, the
volume change was recorded with a reproducibility no lower than 1.5%.
The plasticity Pl of the dispersed paraffin-bearing structures was evaluated by means of
stress-strain (P – ) curves recorded with dP/d  = const (Fig. 2). Plasticity characterizes the ability of the
dispersions to flow, i.e. to undergo very large residual strains without signs of fracture under stresses greater
than the yield point. Plasticity was calculated from the formula:

Δ  m   e
Pl  
ΔP Pm  Pe

Since the elastic strains are typically small for paraffinic petroleum products, the values
of  e and P e can be ignored. In the event of very small elastic strains  e , it can be assumed that  m – e   m . In
this case, Pl =  m/P m = 1/E m . Thus, Pl was approximately evaluated as the inverse modulus of strength or
fracture E m . We chose to use this characteristic as a very approximate but also very simple and convenient
measure of plasticity.
Since the experimental data shows that strength is independent of the loading rate
when dP/d   0.06 N/sec, the measurements were performed using the rate dP/d  = 0.06 N/sec.
The unit described above makes it possible to measure the strength P m (from 0.01 to 7 MPa), volume
shrinkage V, and plasticity Pl of disperse systems cooled at d i ff e r e n t
rates (0.002-0.3 deg/sec) from 130°C to 17°C. We used relatively low cooling rates 0.01-0.05 deg/sec in our
investigation. Strength P m293 was determined at T = 20°C and contraction V Ts293 was determined in the
temperature range from the solidification point T s to 20°C.
We studied the following specimens: factory specimens of solid paraffins obtained from Ozeksuatsk
oil and designated as P-1 (food-grade), T (technical-grade), and Ns (match-grade); test specimens of soft
paraffins from Ozeksuatsk oil (MP-1) and Romashkino oil (MP-2); petroleum ceresines obtained from the
Volgograd Oil Refinery and given the grade designations Ts-65, Ts-75, Ts-80, and Ts-85; petroleum waxes
obtained from the Volgograd refinery and designated as grades Omsk-7 and Omsk-10; protective
wax ZV-1 from the Yaroslavl Oil Refinery.
Table 1 shows the results obtained from investigating the group hydrocarbon composition and
temperature characteristics of the paraffinic petroleum products. The group hydrocarbon composition of the
paraffins was determined by mass spectrometry and gas-liquid chromatography. The content of aromatic
hydrocarbons in the paraffins, ceresines, and waxes was determined based on IR-spectra, while the content
of n-alkanes in the ceresines and waxes was determined by the method of complexing with carbamide.

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Table 1

Content, %
Grade Molecular weight, Melting point n-alkanes (forming
g/mole (dropping point), °C aromatic
a complex with
hydrocarbons
carbamide)
Paraffins
P-1 374.5 55.4 89.46 0.103
Ò 361.4 52.2 87.06 0.835
Ns 338.0 50.0 77.40 1.680
ÌP-1 341.0 45.0 66.50 2.000
ÌP-2 322.0 40.5 63.00 4.000
Ceresines
Ts-65 532.0 70.5 40.80 0.152
Ts -75 520.0 77.5 65.50 0.348
Ts -80 603.0 80.5 60.80 0.506
Ts -85 651.0 115.5 50.40 1.193
Waxes
Omsk -7 500.0 65.0 31.70 1.780
Omsk -10 520.0 68.5 43.30 1.430
ZV-1 420.0 54.5 44.40 0.380

The materials’ temperature characteristics were comparatively evaluated by determining the

paraffins’ melting point in accordance with Zhukov’s method (GOST 4255–75) and the dropping
point (GOST 6793–74) of the ceresines and waxes. The scientific validity and expediency of making such a
comparison is based on the authors’ empirical finding that for all paraffinic petroleum products these
temperatures coincide with the solidification point determined on a bulb thermometer. Thus, paraffins, ceresines,
waxes, and their compounds can be compared to one another by using a single temperature characteristic - the
melting point T s based on drop formation or solidification. Solidification point is determined most easily and
quickly on a bulb thermometer. Thus, this instrument can be used for express evaluations of the fusibility of
paraffinic hydrocarbons and determination of the initial temperature boundary for structure formation. We
established that the strength of the structure formed in petroleum paraffins ~1.5·10 3 Pa at the solidification
point. It is apparent from Table 1 that the highest content of n -alkanes is seen in paraffin of
grade P-1, ceresine of grade Ts-75, and protective wax of grade ZV-1.
The data on the structural-mechanical properties of solid paraffinic petroleum products is generalized
in Table 2. It can be seen that the products which undergo a large amount of contraction generally have
greater strength and less plasticity. The data that has been obtained agrees well with the results of our
studies in regard to the effect of the group composition of paraffins on their structural-mechanical
properties [3]. It was shown that n-alkanes make the largest contribution to the strength of the dispersed
structures of solid paraffins. Impurities in the form of isoalkanes, cycloalkanes, and aromatic hydrocarbons
have a weakening and plasticizing effect, with each of these types of impurities acting independently in
reducing the melting point, strength, and volume shrinkage of paraffins in accordance with the additivity rule.

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 Table 2
Plasticity characteristic
Grade Strength P m293, MPa Contraction VTs293, %
(m/Pm)·10 4, MPa-1
Paraffins
P-1 1.48 17.0 0.37
Ò 1.07 16.6 0.52
Ns 0.76 16.0 1.25
ÌP-1 0.26 12.6 2.90
ÌP-2 0.21 11.3 3.04
Ceresines
Ts-65 0.23 14.0 2.60
Ts -75 0.80 16.5 1.20
Ts -80 0.60 15.8 1.25
Ts -85 1.80 17.0 0.40
Waxes
Omsk -7 0.19 11.5 5.10
Omsk -10 0.14 11.0 6.50
ZV-1 0.45 15.2 1.40

Table 3

Grade m293, MPa

Hard paraffins
P-1 0
Ò 0
Ns 0
Soft paraffins
ÌP-1 0.025
ÌP-2 0.021
Wax es
Omsk -7 0.028
Omsk -10 0.030
ZV-1 0.096
Ceresines
Ts-65 0.108
Ts-80 0.168

The data in Tables 1 and 2 leads to the general conclusion that n-alkanes are the main component
responsible for the strength of all paraffinic petroleum products (paraffins, ceresines, and waxes). The
investigated commercial specimens of paraffins, ceresines, and waxes rank as follows in order
of increasing disperse-structure strength P m 293, increasing contraction, and decreasing plasticity: waxes

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Omsk-10 and Omsk-7, MP paraffin, Ts-65 ceresine, ZV-1 protective wax, Ts-80 ceresine, Ns paraffin,
Ts-75 ceresine, T paraffin, P-1 paraffin, Ts-85 ceresine.
This was the first investigation to establish that many paraffin-bearing systems and petroleum products
become stronger during their loading. Attainment of ultimate strength in such systems is accompanied by an
slow increase in P at a constant rate rather than an unlimited increase in strain  with no change in stress. This
is apparent from Fig. 2 in a comparison of curves OAB’M and OABN. The minimum ultimate strength P m ’ and
the corresponding strain ’ m for the type of systems being discussed correspond to point B’, where the
continuation of the straight flow section B’M separates from the (P –) curve (the curve OAB’M). The
strain-hardening coefficient of the dispersed structure  p is calculated based on the slope tangent tg of the
flow line to the strain axis or the straight line parallel to it:

 p  ΔPΔ

where  p is the increment of stress P referred to the corresponding change in strain .
The factory specimens of ceresines and waxes which had a 40-60% content of hydrocarbons that do
not form complexes with carbamide did undergo strain-hardening during plastic deformation at the breaking
stress. Table 3 shows the strain-hardening coefficient of the dispersed structure of these petroleum
products  m 293 (with the stress increment P m at  = 1 changing from 0.028 to 0.168 MPa). The values of the
coefficient  m 293 of these systems are higher, the greater their molecular weight and strength P m293. The
dispersed structures of individual n-alkanes and cleaned and de-oiled commercial-grade paraffins do not
exhibit a tendency to strain-harden. The presence of more than 5% of an oily phase or aromatic hydrocarbons
in commercial paraffins results in a small amount of strain-hardening  m 293 = 0.03 MPa.
The patterns that have been observed in regard to the strain-hardening of paraffin-bearing structures
are consistent with the dislocation mechanism of this process which was described by Taylor for
metals [4]. In accordance with Taylor’s theory, the strain-hardening of paraffin-bearing structures can be attributed
to the creation of internal stresses which prevent the growth of dislocations. Specifically, strain-hardening takes place
because dislocations combine with one another to form dense pile-ups and are pinned in position by molecules of
impurities. Moreover, since the boundaries of crystals are also an impediment to the movement of dislocations, a greater
tendency to undergo strain-hardening will be exhibited by highly dispersed microcrystalline ceresines and waxes than by
coarse-crystalline paraffins.

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3. Zh. T. Khadisova, E. A. Aleksandrova, and T. P. Fadeeva, Khim. Tekh. Topliv i Masel, No. 3, 45-47 (2004).
4. Rheology (Ed: F. Eyrich) [Russian translation] (Eds.-in-Chief: Yu. N. Rabotnov and P. A. Rebinder). Izd-vo
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