Effect of heat treatment on reactivity-strength of alkali-activated natural pozzolans

Natural pozzolans can be activated and condensed with sodium silicate in an alkaline environment to synthesize high performance cementitious construction materials with low environmental impact. The nature of the starting materials including mineral composition, chemical composition and crystal structure groups affects the formation of the geopolymer gel phase. In this paper, the pozzolanic activities of five natural pozzolans are studied. From XRD and XRF results, most of the raw materials contain zeolite clay minerals and have a high loss on ignition. Therefore, before use, samples were calcined at 700, 800 and 900 °C, respectively. The improvement in pozzolanic properties was studied following heat treatment including calcinations and/or elevated curing temperature by using alkali solubility and compressive strength tests. The results show that pozzolan containing sodium zeolite clinoptilolite can be used to prepare a moderate to high strength binder by heat treatment and calcinations can impart disorder hornblende as a constituent of pozzolan with no amorphous phase to prepare a moderate strength binder.

Oxygen and Chloride Permeability of Alkali-Activated Natural Pozzolan Concrete

One of the important factors in the use of portland cement concrete is its durability, and most of the situations where durability is lacking have been identifi ed and strategies to manage durability have been implemented. Geopolymer concrete, made from an alkali-activated natural pozzolan (AANP), provides an important opportunity for the reduction of carbon dioxide (CO2) emissions associated with the manufacture of concrete but has a limited history of durability studies. Until its different properties are well understood there is no desire to adopt this new technology of unknown provenance by the concrete industry. This paper presents an experimental study of oxygen and chloride permeability of AANP concrete prepared by activating Taftan andesite and Shahindej dacite (Iranian natural pozzolans), with and without calcining, and the correlations between these properties and compressive strength. The results show that compared to ordinary portland cement (OPC) concrete, AANP concrete has lower oxygen permeability at later ages; but it shows moderate to high chloride ion penetrability.

Alkali-Activated Natural Pozzolan Concrete as New Construction Material

In the near future, geopolymers or alkali-activated cementitious materials will be used as new high-performance construction materials of low environmental impact with a reasonable cost. This material is a good candidate to partially replace ordinary portland cement (OPC) in concrete as a major construction material that plays an outstanding role in the construction industry of different structures. Geopolymer materials are inorganic polymers based on alumina and silica units; they are synthesized from a wide range of dehydroxylated alumina-silicate powders condensed with alkaline silicate in a highly alkaline environment. Geopolymeric materials can be produced from a wide range of alumina-silica, including natural products--such as natural pozzolan and metakaolin--or coproducts--such as fly ash (coal and lignite), oil fuel ash, blast furnace or steel slag, and silica fume--and provide a route toward sustainable development. Using lesser amounts of calcium-based raw materials, lower manufacturing temperature, and lower amounts of fuel result in reduced carbon emissions for geopolymer cement manufacture up to 22 to 72% in comparison with portland cement. A study has been done by the authors to investigate the intrinsic nature of different types of Iranian natural pozzolans to determine the activators and methods that could be used to produce a geopolymer concrete based on alkali-activated natural pozzolan (AANP) and optimize mixture design. The mechanical behavior and durability of these types of geopolymer concrete were investigated and compared with normal OPC concrete mixtures cast by the authors and also reported in the literature. This paper summarizes the main conclusions of the research regarding pozzolanic activity, activator properties, engineering and durability properties, applications and evaluation of carbon footprint, and cost for AANP concrete.

Simplified model for prediction of compressive strength of alkali-activated natural pozzolans

The assessment of pozzolanic activity is essential for estimating the reaction of a material as pozzolan. Natural pozzolans can be activated and condensed with sodium silicate in an alkaline environment to synthesize high performance cementitious construction materials with low environmental impact. In this paper, the pozzolanic activities of five natural pozzolans are studied. The correlation between type and chemical composition of natural pozzolan, which affects the formation of the geopolymer gel phase, both for the calcined and untreated natural pozzolans, have been reviewed. The improvement in pozzolanic properties was studied following heat treatment including calcinations and/or elevated curing temperature by using alkali solubility, and compressive strength tests. A model was developed to allow prediction of the alkali-activated pozzolan strength versus their chemical compositions, alkali solubility, and crystallinity.

Otimização e análise mecânica de pastas geopoliméricas para uso em poços sujeitos à injeção cíclica de vapor

Oil wells subjected to cyclic steam injection present important challenges for the development of well cementing systems, mainly due to tensile stresses caused by thermal gradients during its useful life. Cement sheath failures in wells using conventional high compressive strength systems lead to the use of cement systems that are more flexible and/or ductile, with emphasis on Portland cement systems with latex addition. Recent research efforts have presented geopolymeric systems as alternatives. These cementing systems are based on alkaline activation of amorphous aluminosilicates such as metakaolin or fly ash and display advantageous properties such as high compressive strength, fast setting and thermal stability. Basic geopolymeric formulations can be found in the literature, which meet basic oil industry specifications such as rheology, compressive strength and thickening time. In this work, new geopolymeric formulations were developed, based on metakaolin, potassium silicate, potassium hydroxide, silica fume and mineral fiber, using the state of the art in chemical composition, mixture modeling and additivation to optimize the most relevant properties for oil well cementing. Starting from molar ratios considered ideal in the literature (SiO2/Al2O3 = 3.8 e K2O/Al2O3 = 1.0), a study of dry mixtures was performed,based on the compressive packing model, resulting in an optimal volume of 6% for the added solid material. This material (silica fume and mineral fiber) works both as an additional silica source (in the case of silica fume) and as mechanical reinforcement, especially in the case of mineral fiber, which incremented the tensile strength. The first triaxial mechanical study of this class of materials was performed. For comparison, a mechanical study of conventional latex-based cementing systems was also carried out. Regardless of differences in the failure mode (brittle for geopolymers, ductile for latex-based systems), the superior uniaxial compressive strength (37 MPa for the geopolymeric slurry P5 versus 18 MPa for the conventional slurry P2), similar triaxial behavior (friction angle 21° for P5 and P2) and lower stifness (in the elastic region 5.1 GPa for P5 versus 6.8 GPa for P2) of the geopolymeric systems allowed them to withstand a similar amount of mechanical energy (155 kJ/m3 for P5 versus 208 kJ/m3 for P2), noting that geopolymers work in the elastic regime, without the microcracking present in the case of latex-based systems. Therefore, the geopolymers studied on this work must be designed for application in the elastic region to avoid brittle failure. Finally, the tensile strength of geopolymers is originally poor (1.3 MPa for the geopolymeric slurry P3) due to its brittle structure. However, after additivation with mineral fiber, the tensile strength became equivalent to that of latex-based systems (2.3 MPa for P5 and 2.1 MPa for P2). The technical viability of conventional and proposed formulations was evaluated for the whole well life, including stresses due to cyclic steam injection. This analysis was performed using finite element-based simulation software. It was verified that conventional slurries are viable up to 204ºF (400ºC) and geopolymeric slurries are viable above 500ºF (260ºC)

Influência da adição de cálcio nas propriedades de pastas geopoliméricas destinadas a cimentação de poços de petróleo

Nowadays, the search for new technologies that are able to follow the upcoming challenges in oil industry is a constant. Always trying properties improvements of the used materials, looking for the best performance and greater life time. Besides the search for technologies that show an improvement of performance, the search for materials environmentally correct along the whole production process. In Oil well cementing, this search for new technologies passes through the development of slurry systems that support these requests and that are also environmentally friendly. In this context, the use of geopolymer slurries is a great alternative route to cementing oil wells. Besides having good properties, comparable to Portland cement slurries, this alternative material releases much less CO2 gas in the production of their root materials when compared the production of Portland cement, which releases tons of CO2. In order to improve the properties of geopolymer slurries has been added Calcium Oxide, as observed in other studies that slurries where the Calcium is present the values of compressive strength is greater. The addition has been realized based in the CaO/SiO2 molar ratio of 0.05, 0.10 and 0.15. Have been performed compressive strength tests, thickening time, rheology and fliud loss control test of the slurries, following NBR 9831, as well as the physical chemical characterization of XRD, SEM and TG. Has been observed in most of the tests the slurries follow a tendency until the ratio of 0.10, which inverses in the ratio 0.15. This behavior can be explained by two phenomena that occur simultaneously, the first one is the break of the polymer chains and a consequent increase in molucules mobility, which prevails until the ratio of 0.1, and the second is possible approach of the chains due to the capacity of the calcium ions stabilize the charges of two different aluminum. There is only one linearity in the mechanical behavior that can be attributed to the appereance of the C-S-H phase. Based on this, it is concluded that the phenomenon of breaking the polymer chains predominates until the ratio of 0.1, causing an increase of the filtrate volume, lower rheological parameters and increasing thickening time. From the ratio of 0.15 the approach of the chains predominates, and the behavior is reversed

Adição de resíduo cerâmico em pastas geopoliméricas para cimentação de poços de petróleo

The development of activities the of oil and gas sector have promoted the search for suitable materials for cementing oil wells. In the state of the Rio Grande do Norte, the integrity of the cement sheath tends to be impaired during steam injection, a procedure necessary to increase oil recovery in reservoirs with low-viscosity oil. The geopolymer is a material that can be used as alternative cement, since it has been used in the production of fire-resistant components, building structures, and for the control of toxic or radioactive residues. Geopolymers result from condensation polymer alkali aluminosilicates and silicates resulting three-dimensional polymeric structures. They are produced in a manner different from that of Portland cement, which is made an activating solution that is mixed with geopolymer precursor. Among the few works studied allowed us to conclude that the pastes prepared with metakaolin as precursor showed better performance of its properties. Several studies show the addition of waste clay as a means of reducing cost and improving end of the folder properties. On this basis, the goal is to study the influence of the addition of ceramic waste in geopolymer paste. To develop the study of rheology tests were carried out, filtered, thickening time, compressive strength, free water, specific gravity and permeability, according to the American Pretoleum Institute (API). The results for all formulations studied show that the folders have high mechanical strength to a light paste; low filtrate volume, absence of free water, very low permeability, slurry, consistent with a light paste, and thickening time low that can be corrected with the use of a retardant handle. For morphological characterization, microstructural, physical, chemical and thermal tests were carried out by XRD, MEV, DTA, TG, FTIR. In the trial of XRD, it was found that geopolymer is an amorphous material, with a peak of crystalline kaolinite. In tests of TG / DTA, revealed the presence of a significant event, which represents the mass loss related to water, and also observed the reduction of weight loss by increasing the concentration of ceramic waste. In the trial of MEV, we found a uniform matrix without the presence of other phases. In the trial of FT-IR, we observed the presence of the band related to water. From all results it was determined that the optimum concentration range of use is between 2.5 and 5% of waste ceramic

Desenvolvimento de um sistema misto de pasta à base de geopolímero e cimento portland para correção de perda de circulação

The materials engineering includes processes and products involving several areas of engineering, allowing them to prepare materials that fulfill the needs of various new products. In this case, this work aims to study a system composed of cement paste and geopolymers, which can contribute to solving an engineering problem that directly involves the exploitation of oil wells subject to loss of circulation. To correct it, has been already proposed the use of granular materials, fibers, reducing the drilling fluid or cement paste density and even surface and downhole mixed systems. In this work, we proposed the development of a slurry mixed system, the first was a cement-based slurry and the second a geopolymer-based slurry. The cement-based slurry was formulated with low density and extenders, 12.0 ppg (1.438 g/cm ³), showing great thixotropic characteristics. It was added nano silica at concentrations of 0.5, 1.0 and 1.5 gps (66.88, 133.76 and 200.64 L/m3) and CaCl2 at concentrations of 0.5, 1, 0 and 1.5%. The second system is a geopolymer-based paste formulated from molar ratios of 3.5 (nSiO2/nAl2O3), 0.27 (nK2O/nSiO2), 1.07 (nK2O/nAl2O3) and 13.99 (nH2O/nK2O). Finally, we performed a mixture of these two systems, for their application for correction of circulation lost. To characterize the raw materials, XRD, XRF, FTIR analysis and titration were performed. The both systems were characterized in tests based on API RP10B. Compressive strength tests were conducted after curing for 24 hours, 7 and 28 days at 58 °C on the cement-based system and the geopolymer-based system. From the mixtures have been performed mixability tests and micro structural characterizations (XRD, SEM and TG). The results showed that the nano silica, when combined with CaCl2 modified the rheological properties of the cement slurry and from the concentration of 1.5 gpc (200.64 L / m³) it was possible to obtain stable systems. The system mixture caused a change in the microstructure of the material by favoring the rate of geopolymer formation to hinder the C3S phase hydration, thus, the production of CSH phases and Portlandite were harmed. Through the mixability tests it can be concluded that the system, due to reduced setting time of the mixture, can be applied to plug lost circulation zones when mixed downhole

Aditivação de pastas geopoliméricas com tetraborato de sódio e látex não iônico para cimentação de Poços de Petróleo

The development of activities in the oil and gas sector has been promoting the search for materials more adequate to oilwell cementing operation. In the state of Rio Grande do Norte, the cement sheath integrity tend to fail during steam injection operation which is necessary to increase oil recovery in reservoir with heavy oil. Geopolymer is a material that can be used as alternative cement. It has been used in manufacturing of fireproof compounds, construction of structures and for controlling of toxic or radioactive waste. Latex is widely used in Portland cement slurries and its characteristic is the increase of compressive strength of cement slurries. Sodium Tetraborate is used in dental cement as a retarder. The addition of this additive aim to improve the geopolymeric slurries properties for oilwell cementing operation. The slurries studied are constituted of metakaolinite, potassium silicate, potassium hydroxide, non-ionic latex and sodium tetraborate. The properties evaluated were: viscosity, compressive strength, thickening time, density, fluid loss control, at ambient temperature (27 ºC) and at cement specification temperature. The tests were carried out in accordance to the practical recommendations of the norm API RP 10B. The slurries with sodium tetraborate did not change either their rheological properties or their mechanical properties or their density in relation the slurry with no additive. The increase of the concentration of sodium tetraborate increased the water loss at both temperatures studied. The best result obtained with the addition of sodium tetraborate was thickening time, which was tripled. The addition of latex in the slurries studied diminished their rheological properties and their density, however, at ambient temperature, it increased their compressive strength and it functioned as an accelerator. The increase of latex concentration increased the presence of water and then diminished the density of the slurries and increased the water loss. From the results obtained, it was concluded that sodium tetraborate and non-ionic latex are promising additives for geopolymer slurries to be used in oilwell cementing operation

An Investigation of Waste Glass-Based Geopolymers Supplemented with Alumina

An increased consideration of sustainability throughout society has resulted in a surge of research investigating sustainable alternatives to existing construction materials. A new binder system, called a geopolymer, is being investigated to supplement ordinary portland cement (OPC) concrete, which has come under scrutiny because of the CO2 emissions inherent in its production. Geopolymers are produced from the alkali activation of a powdered aluminosilicate source by an alkaline solution, which results in a dense three-dimensional matrix of tetrahedrally linked aluminosilicates. Geopolymers have shown great potential as a building construction material, offering similar mechanical and durability properties to OPC. Additionally, geopolymers have the added value of a considerably smaller carbon footprint than OPC. This research considered the compressive strength, microstructure and composition of geopolymers made from two types of waste glass with varying aluminum contents. Waste glass shows great potential for mainstream use in geopolymers due to its chemical and physical homogeneity as well as its high content of amorphous silica, which could eliminate the need for sodium silicate. However, the lack of aluminum is thought to negatively affect the mechanical performance and alkali stability of the geopolymer system. Mortars were designed using various combinations of glass and metakaolin or fly ash to supplement the aluminum in the system. Mortar made from the high-Al glass (12% Al2O3) reached over 10,000 psi at six months. Mortar made from the low-Al glass (<1% Al2O3) did not perform as well and remained sticky even after several weeks of curing, most likely due to the lack of Al which is believed to cause hardening in geopolymers. A moderate metakaolin replacement (25-38% by mass) was found to positively affect the compressive strength of mortars made with either type of glass. Though the microstructure of the mortar was quite indicative of mechanical performance, composition was also found to be important. The initial stoichiometry of the bulk mixture was maintained fairly closely, especially in mixtures made with fine glass. This research has shown that glass has great potential for use in geopolymers, when care is given to consider the compositional and physical properties of the glass in mixture design.