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Portland cement for the cementing of oil wells developed with the aid
of the Rietveld refinement method
Danielle do N. S. Oliveira1, Gelmires de A. Neves 2, Ulisses T. Bezerra3, Alexsandra C.
Chaves4, Bruna S. Lira5
1. Federal University of Campina Grande, Brazil, daninascimento.eng@gmail.com
2. Federal University of Campina Grande, Brazil, gelmires@dema.ufcg.edu.br
3. Federal Institute of Education, Science and Technology of Paraíba, Brazil, dartarios@yahoo.com.br
4. Federal University of Campina Grande, Brazil, alexsandrachaves@hotmail.com
5. Federal University of Campina Grande, Brazil, brunaslira@gmail.com
Abstract
The use of the Rietveld refinement method has been highlightened as essential in the
characterization of polycrystalline materials. With the aid of this method, combined with
the application of the X-ray diffraction, it was possible to develop a type of cement that
can temporarily substitute the Portland cement for Oil well. This cement was developed
from the mixture of Portland cements commonly found in the market. The cements were
passed through various sieves, then characterized by X-ray diffraction, being identified
the main phases (C3A, C4AF, C3S and C2S) and quantified by the Rietveld refinement
method. With the values obtained in the quantification of the phases, a new cement was
made through the method of linear programming. From the results, it was possible to
conclude that the developed cement presented a composition (levels of the main
phases) that satisfies the requirements of NBR 9831, mainly in relation to the low levels
of C3A.
Keywords: Rietveld refinement; X-ray diffraction; Portland cement for oil well.
Introduction
derived from the sample structure and the geometry of the X-ray diffractometer.
Furthermore, the method consents the definition of Bragg reflection’s positions and
intensities, so that, even if there is peak overlap, the reflection intensities of each phase
can be evaluated with good precision, allowing more precision in the quantitative
analysis results [3].
The microstructure of a material, in other words, the types, quantities and
distribution of its constituent phases, are intimately related with the processes that form
the material and its properties [4]. To Bezerra [5], the cements of general use are
differentiated from the ones intended for oil well cementation by the control adopted in
the fabrication process and also by the contents of the four basic components of the
Portland cement (C2S, C3S, C3A e C4AF). Among them, the one that deserves more
attention is the C3A, as, its hydration and hardening properties are directly related to its
concentration [6], in addition to being responsible for the materials resistance to sulfates.
For the cementation of oil wells a cement paste basically made of cement, water
and additives is used. The cement used for this operation is a specific type of Portland
cement that, according to Saoût et al. [7], is capable of providing to the paste a low
viscosity, leaving it pumpable to be used in high depths where high temperatures and
pressure are found.
The cementation of the wells stage is extremely important, because the main
objective of placing the cement paste in the annular space between the casing tube and
the stone formation is the zonal isolation, in other words, the annular cement sheath
must isolate zones that contain pressurized fluids and maintain the isolation, even when
the cement sheath is susceptible to tension changes during the operational life of the
well [8]. To support the severe environments to which the wells are exposed, the
cements used in the cementation must provide a larger uniformity, more controlled
physical and chemical properties, more compatibility with additives and better stability in
the storage.
Between the nine classes (named from A to J) which are divided the Portland
cements for oil wells, classes G and H are the most wildly used in the world [9]. In Brazil,
a cement very similar to class G is used, called Portland Cement Special Class.
Therefore, the aim of this study was to develop a type of cement capable of
replacing the class G Portland cement for oil wells, with the aid of the Rietveld
refinement method (conducted through the TOPAS program), allied to the application of
the X-ray diffraction and the use of the electronic spreadsheet Solver.
In this case, the Rietveld refinement was used with the finality of verifying if there
is a separation of the present phases in the cement when submitted to sieving through
the quantification of the portions of each phase that were retained in each sieve and the
potions that passed. Besides that, the data also served to feed the Solver software.
(ii) Portland cement CP III 40 RS (Blast furnace slag Portland cement – Sulfate
Resistant); and
(iii) Portland cement CP IV 32 RS (pozzolanic Portland cement – sulfate resistant).
The cements were submitted to a prior sieving and each sieve fraction was
analyzed by X-ray diffraction, having its phases quantified by the Rietveld method,
through the TOPAS program, that indicated the quantity of each one of the main phases
present in the cement, specifically the C3A, the C2S, the C3S and the C4AF.
The data obtained from the quantitative of each phase of the sieved fractions of
the cements served to feed the Solver program of an electronic spreadsheet, which
works with the principal of Linear programing that determined the composition of the
new cement. The restrictions were made according to the specifications of NBR 9831
[10] for Portland cement for oil well class G.
(a)
IPMM 2012
7th International Conference on Intelligent Processing and
Manufacturing of Materials
September, 2-3, 2012, Foz do Iguaçu, Brazil
(b)
(c)
Figure 1. X-ray diffraction of the sieved cements: (a) CP II; (b) CP III; (c) CP IV.
Analyzing Figure 1(a), it was observed that, as expected, there were selection of
some compounds with the sieving. This selection can be observed comparing the
intensity of the peaks of each compound, for example, the plaster (CaSO42H2O) peaks
that appeared more intensely in the background of the sieve that, probably, implies a
higher presence of this compound. Because, the amplitudes of the diffractograms
peaks, besides guarding a characteristic relation of the crystalline structure of each
phase that composes the sample, reflect the proportion of the phases in the same [1].
By analyzing Figure 1(b), it was verified that in the background of the sieve was
retained a larger quantity of alite and plaster. In Figure 1(c), the peak located in the
IPMM 2012
7th International Conference on Intelligent Processing and
Manufacturing of Materials
September, 2-3, 2012, Foz do Iguaçu, Brazil
interplanar distance of 26.72 Å that, probably, is quartz (SiO2), that is retained in larger
quantity or in more crystalline form in ABNT sieve no 325 (0.045 mm).
Table 1 and Figure 2, presented the results of the quantitative analyses of the
Portland cements (CP II, CP III and CP IV, respectively) performed by TOPAS (using the
Rietveld method), of the pure cements (not sieved) and the portions retained in the
ABNT sieves no 200 (0.074 mm) and no 325 (0.045 mm) as well as the portions passed
through ABNT sieve no 325 (0.045 mm) (background).
Analyzing Table 1, it can be observed that, with the sieving, there is a separation
of the constituent phases of the cements with some defined tendencies. Figure 2
illustrates with more precision this collocation.
IPMM 2012
7th International Conference on Intelligent Processing and
Manufacturing of Materials
September, 2-3, 2012, Foz do Iguaçu, Brazil
(a) (b)
(c)
Figure 2. Quantification of phases: (a) Portland cement CP II sieved; (b) Portland cement CP III sieved; (c)
Portland cement CP IV sieved.
In Figure 2, it can be observed that the higher content of C3S passed through the
set of sieves (ABNT nº 200 and ABNT no 325), which showed that it is a phase
composed, mostly, by small particles, this can be better observed in Figure 2b, referring
to the Portland cement CP III. Another fact that requires attention relates to the content
of C3A. In the CP II and CP III cements (referring to Figures 2a and 2b), this phase has
larger grains that were retained in sieve no 200. In the CP IV cement, this phase
presented smaller particles that passed through the sieves and were retained in the
background of the sieves. Comparing the three cements it was noticed that the CP II
was the most sensible to the sieving, because the inclination of the lines (angular
coefficient) of their components proved to be more accentuated than the others.
With the data provided from the quantitative analyses of the phases (Rietveld
method), the SOLVER program electronic spreadsheet determined an ideal mixture for
IPMM 2012
7th International Conference on Intelligent Processing and
Manufacturing of Materials
September, 2-3, 2012, Foz do Iguaçu, Brazil
the obtainment of the new cement. The answer provided by the program was equivalent
to a Portland cement for oil well class G with Medium Resistance to Sulfates (MRS) as
shown in Table 2, because for the Portland cement for oil well class G with High
Resistance to Sulfates (HRS), the program did not define an ideal composition, due to
the non-compliance of the specifications regulated by NBR 9831 [10]: C4AF+2C3A>24%.
According to the report from Table 2, the new cement was composed by 47.4% of
CP III cement retained in sieve no 200 and 52.6% of CP III that passed through sieve no
325. As previously mentioned, this composition meets the specifications of NBR 9831
[10] for the for Portland cement for oil well class G, with medium resistance to sulfates,
which is satisfactory for the conditions of the most common oil wells of Brazil.
The composition of the new cement provided by the Solver can be observed in
Table 3, where the main phases of the produced cement are exposed.
Table 2. Quantification of the Portland cement for oil well phases by the Solver.
Phases Quantity (%)
Cement class G New cement
(MRS)*
C3S 48 – 58 57,13
C2S - 12,20
C3A <8 3,92
C4AF - 26,74
C4AF+2.C3A - 34,59
* Specification of standard NBR 9831 [10].
According to Table 3, it can be observed that the new cement met the
specifications of NBR 9831 [10] that determines the proportions of the main phases of
the Portland cement for oil wells, especially in relation to the low content of C3A,
compound responsible for the initial setting time of the cement.
IPMM 2012
7th International Conference on Intelligent Processing and
Manufacturing of Materials
September, 2-3, 2012, Foz do Iguaçu, Brazil
Conclusions
The results obtained were satisfactory, because they showed the use of the
refinement by the Rietveld method.
The simple sieving of the cement causes there to be a certain separation of the
phases, the CP III being the most sensitive to this fractionation.
The developed cement presented a composition (content of the main phases)
that meets the specifications of NBR 9831.
Acknowledgments
References