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VII Congresso Brasileiro de Análise Térmica e Calorimetria 25 a 28 de Abril de 2010 – São Pedro – SP - Brasil


R. F. Correia 1, C. A. A. Rocha 1, Jo Dweck 2, R. D. Toledo Filho1, E. M. R. Fairbairn1

COPPE/UFRJ - Programa de Engenharia Civil, Rio de Janeiro, Brasil,,,,

EQI/UFRJ – Departamento de Processos Inorgânicos, Rio de Janeiro, Brasil,

Abstract This work presents a study by thermogravimetric analysis (TG and DTG) and compressive strength of four oil well cement slurries. They were cured at a temperature of 60ºC under different pressures: 0 MPa, 6.89 MPa, 20.68 MPa and 31.03 MPa, It was checked by thermogravimetry that the hydrated components are the same than the slurry cured at 0 MPa. The amounts of calcium hydroxide formed in the slurries tend to be smaller for those curedat higher pressures, but the results of compressive strength and Young module didn’t show a significant difference. Key-words: Well cementation, hydration cement, thermogravimetric analysis. 1. INTRODUCTION The objective of cementing the annulus between the well casing and the rock formation is to provide zonal isolation and structural support as well. Oil wells are drilled at high depths and this imposes high pressure and different temperature gradients. Due to this ambient the cementitious material should be prepared and tested with the same field conditions. Laboratory tests are realized with pressure and temperature to determine the mechanical and durability properties. However some studies have been realized with and without pressure to check the influence of this variable in the material proprieties. The temperature influence already been known of the literature (NELSON, 1990; NEVILLE, 1997; MEHTA & MONTEIRO, 1994). About cure under pressure there are studies at working pressures from 0 MPa up to 344 MPa (BAJZA et al., 1975; ROY et al., 1972 e LE SAOUT et al., 2006). These studies show that the cure under high pressures affects the compressive strength, increasing it and reducing the porosity of material. Nevertheless Zhou & Beaudouin (2003) studied the effects of 6.8 MPa pressure in hydration of Portland cement and they concluded that it didn’t have a significant difference on the final density of the cement hydration products between the materials cured with and without this pressure. Therefore the studies presented didn’t establish clearly the relation between ranges of pressure that affect the cement hydration on the mechanical and durability proprieties. Thus, this work aims to evaluate the influence of the pressure on the cure at four pressures: 0 MPa, 6.89 MPa, 20.68 MPa and 31.03 Mpa by thermogravimetric analysis and compressive strength. 3. MATERIALS AND METHODS 3.1. Materials The materials used in the slurries were: Class G cement, water and superplasticizer. The cement’s composition in oxides, measured by X-Ray Fluorescence Spectrometry (XRF) was: CaO – 67,4%; SiO2 – 18,0%; Fe2O3 – 5,4%; Al2O3 – 4,1%; SO3 – 3,9%; and 1,4% of other minor components.

RESULTS 4. Subsequently. Methods of prepare the slurries and cure of the samples The slurries were prepared following the procedure described in NBR 9831 (2006). 4. Nitrogen with a flow of 100 mL min-1 was used as purge gas and platinum pans were used . Therefore the products of cement hydration formed in all slurries were the same. Compressive Strength For the compressive strength three cylindrical samples. After this period the autoclave was turned off and the samples remained for 24 hours inside it. The table shows the amounts of calcium hydroxide (Ca(OH)2). temperature which was maintained for 1 hour to dry the sample. .68 / 3000 31. with 50mm of diameter and 100mm of height. Cure conditions Pressure (MPa/psi) 0 6.1.03 / 4500 Temperature (ºC) 60ºC 60ºC 60ºC 60ºC Name P0 P1000 P3000 P4500 3. Thermogravimetric Analysis The thermogravimetric analyses were realized in SDT Q600 TGA/DTA/DSC from TA Instruments.VII Congresso Brasileiro de Análise Térmica e Calorimetria 25 a 28 de Abril de 2010 – São Pedro – SP .89 / 1000 20.3. 3. Each sample was heated at from room temperature up to 35ºC. P1000.2. P3000 and P4500 slurries. Moreover the samples were cured in an autoclave at 60ºC and pressures according to the table 1 for six days. The samples were tested in a Shimadzu UH-F1000 kN and two Linear Variable Differential Transformers (LVDT) also were used to measure the displacement. 2009). It can be seen that there is a tendency to reduce the amount of Ca(OH)2 with increasing pressure. They were calculated initially on calcined mass basis and afterwards on initial cement mass basis as suggested by Dweck (2000. Thermogravimetric Analysis The figure 1 show the results of thermogravimetric analyses realized for P0. in other words. However the amount these products presented differed slightly in relation to mass loss when pressure was applied. it was heated to 1000° C at a heating ratio of 10ºC/min. Table 1. were used for each slurry. The analyses were performed for original cement and for the solidified bodies obtained from P0. only P3000 behaves differently.Brasil 2/4 3. This procedure was done to cool the samples to atmosphere temperature. Variance analysis with 5% of probability was used. it presented a lesser amount of Ca(OH)2 than P4500.4. The phases found in slurries submitted to pressure were the same to those without pressure.

Mechanical Proprieties Table 3 shows medium values of compressive strength and Young Modulus.36 – 0.75 Compression strength (MPa) 45 44 43 42 41 40 P0 P1000 P3000 P4500 Pressure level 10 8 Figure 2 .09 – 8.Brasil Comment: P0 06/11/2009 Rosana Instrument: SDT Q600 V20.66 17.0 1000 Universal V4.13 – 1.5 50 401.31 3. Figure 2 presents a graph with such variables. Through thermogravimetric analyses it was possible to calculate the amount of Ca(OH)2 in the slurries. 4. Weight (%/min) 1. The hydrated calcium silicates are responsible for the mechanical strength of material.05 15. % of calcium hydroxide on calcined base. 5. it is possible to identify a soft tendency of decrease value with pressure increase. It was checked the tendency of decreasing content of Ca(OH)2 with pressure increase.0 Sample Cement P0 P1000 P3000 Mass loss* (H2O) (%) 0.28 3.30 3. However this result didn’t influence significantly in the compressive strength and Young Modulus.54 – 3.91 – 1.24°C 80 Weight (%) 1.3.08 14. Nevertheless the compressive strength and the content of Ca(OH)2 present in the slurries.P0 case. Therefore it’s possible Calcim hydroxide (%) .VII Congresso Brasileiro de Análise Térmica e Calorimetria 25 a 28 de Abril de 2010 – São Pedro – SP .26 * .15 44. [ – – – – ] Deriv. Both compressive strength and Young Modulus didn’t present a significant difference among the studied cases. which indicates that the change of pressure up to the maximum studied level didn’t influence the mechanical properties.5 Build 15 3/4 100 P0 90 430.13 43.12% 60 0.5 Table 2. CONCLUSION The amount of Ca(OH)2 is linked with the hydration level of cementitious material because its production is simultaneous to the generation of hydrated calcium silicates.62 70 70.35° C 3.51 – 1.41 14.03 Ca(OH)2 (%) 17.67 P4500 3.450% 0 200 400 600 Temperature (°C) 800 40 0.47 Young Modulus E (GPa) – CV (%) 14.Compression strength and calcium hydroxide content as a function of pressure.Mass loss of H2O due to CH dehydration Figure 1 – Typical TG and DTG curves . These mechanical properties do not present significant difference in the analyzed pressure levels.31 – 5.4A TA Instruments 16.10 45.49 – 1. Mechanical proprieties Sample P0 P1000 P3000 P4500 Compressive Strength fc (MPa) – CV (%) 45.00 14. 46 20 18 16 14 12 Compression strength Calcium hydroxide Table 3. when compared to each other.

ROY. 2003. São Paulo: Ed.. pp 828.A. J.CUNHA. Cement and Concrete Research. vol. J. D. Thermogravimetry on calcined mass basis – hydrated cement phases and pozzolanic activity quantitative analysis. BEADOIN. F. RIVEREAU.. 2 pp.1007/s10973-008-9761-0. DWECK. J.. G. LÉCOLIER. M. São Paulo: Pini.. 2009. p. NELSON. 1972. PINTO. 2.. Q. COELHO A. A. LE SAOUT. C. ZHOU. I Class G oilwell cement. E..M. J.. 2006. Hydration of a Portland cement blended with calcium carbonate. propriedades e materiais. S. Cement and Concrete Research. J. J. Rio de Janeiro.. SALAJ. Effect of applied hydrostatic stress on the hydration of Portland cement and C3S. 1. Thermochemical Acta. 36 pp. 497 – 502. 1994. P. MONTEIRO. 1975. BAJZA. 71 – 78. Term. 6. D. Calorim. Autoclaved compressed cement pastes. n 1. Giammusso. P. A. BÜCHLER. Chemical structure of cement aged at normal and elevated temperatures and pressures Part.VII Congresso Brasileiro de Análise Térmica e Calorimetria 25 a 28 de Abril de 2010 – São Pedro – SP . vol. C. vol. DWECK. . P. 1990. Schlumberger Educational Services. (On-line) DOI:10. vol 15. 7. 346.. pp 9-16. M.. Cimento Portland destinado à cimentação de poços petrolíferos – Requisitos e métodos de ensaio: NBR 9831. GOUDA. 2006. KUSÝ. A. Propriedades do Concreto. 349 – 366.. REFERENCES ASSOCIAÇÃO BRASILEIRA DE NORMAS TÉCNICAS. K. n. Concreto: estrutura. Houston. Cement and Concrete Research. CARTLEDGE. Well Cementing. Trad. MEHTA. BOBROWSKY. J. P. Pini. 5 pp.ed. B. Anal. H.Brasil 4/4 to conclude that the studied pressures softly affect the hydration of cement but significant for the affect of the mechanical proprieties.. M. Advances in Cement Research.P. GONÇALVES.M. ZANNI. G.... NEVILLE. A. Salvador E. 105 – 113.C. A.. BUCHLER. K. A. R... 1997.. E. GEBE. pp 616. 2000.L. V. Very high strength cement pastes prepared by hot pressing and other high pressure techniques. ACKNOWLEDGEMENTS The authors would like to acknowledge the Brazilian National Council of Research and Development (CNPq) and Coordination for the Improvement of Higher Education (CAPES)...