Effect of partial replacement of geopolymer binder materials on the fresh and mechanical properties: A review

The growth of demand for concrete raises concerns about the consumption of natural resources and ordinary Portland cement. Geopolymer composites show promise as a sustainable alternative for conventional cement concrete. Considering the wide range of potential geopolymer composites applications (including suitability for transportation infrastructure, underwater applications, repair and rehabilitation of structures as well as recent developments in 3D printing), the desired fresh and mechanical properties of the geopolymer composite may vary between applications: for example, rapid setting can be a merit for certain applications and a demerit for others. Therefore, the desired fresh and mechanical properties (e.g., workability, setting time, compressive strength, etc.) can be controlled for a given geopolymer source material through its partial substitution by natural or by-product materials. Recognizing the critical role of various replacement materials in enhancing the potential applications of geopolymer composites, the present review was undertaken to quantify and understand the effect of partial replacement by fly ash, metakaolin, kaolin, red mud, slag, ordinary Portland cement, and silica fume on the setting time, workability, compressive strength and flexural strength of various source materials addressed in the literature. The review also provides insights into research gaps in the field to promote future research.     

Kinetochemical and morphological differentiation of ettringites by the Le Chatelier-Anstett test

In this research, former XRD experiments have been verified by Le Chatelier-Ansttet (L-A) test. For this purpose, 28 cements consisting of 7 Portland cements and 21 blended cements containing 20%, 30% and 40% metakaolin have been submitted to the Le Chatelier-Anstett (L-A) test for 2 years. With all these cements, L-A specimens were manufactured and a direct parameter was measured for these specimens: increase in diameter, Δ∅, or diameter growth. Other complementary determinations were chemical analysis, XDA patterns and SEM of ettringites and specific properties of some cements tested. The experimental results have borne out that the formation rate of the ettringite formed from the reactive alumina, Al₂O₃^r−, present in pozzolans must be considerably higher than the formation rate of the ettringite from C₃A and much higher than the ettringite from C₄AF, both present in OPC. Owing to this, these ettringites were proposed being named “rapid formation” (ett-rf), “slow formation” (ett-lf) and “very slow formation” (ett-vlf) ettringites, respectively. On the other hand, these experimental results have also shown that the ett-rf has a much smaller size than the ett-lf (this is a direct consequence of the aforementioned conclusion); that almost all the alumina, Al₂O₃, present in M pozzolan must be regarded as being “reactive,” Al₂O₃^r−, or at least, the greatest part; that the detrimental effects derived from gypsum attack are shown much earlier in these POZC than in their plain OPC and, to such an extent, that this aggressive action can be described as rapid gypsum attack; and that none of the 21 POZC tested can be described as high nor moderate sulphate resistant cements according to L-A test.     

偏高岭土及其对油井水泥性能的影响

综述了偏高岭土特性及其在水泥混凝土领域中的应用情况,初步研究了偏高岭土对油井水泥性能的影响。结果表明,偏高岭土能显著提高油井水泥的抗压强度,表现出很强的火山灰活性,完全可以作为新一代的油井水泥掺合料。     

Reactive pozzolana from Indian clays—their use in cement mortars

Studies were undertaken to produce reactive pozzolana i.e. metakaolin from four kaolinitic clays collected from different sources in India. The metakaolin produced from these clays at 700-800 °C show lime reactivity in between 10.5 to 11.5 N/mm² which is equivalent to commercially available calcined clay Metacem-85. The microstructure of the metakaolin has been reported. The effect of addition of metakaolin up to 25% in the Portland cement mortars was investigated. An increase in compressive strength and decrease of porosity and pore diameter of cement mortars containing metakaolin (10%) was noted over the cement mortars without metakaolin. The hydration of metakaolin blended cement mortars was investigated by differential thermal analysis (DTA) and scanning electron microscopy (SEM). The major hydraulic products like C-S-H and C₄AH₁₃ have been identified. Durability of the cement mortars with and without metakaolin was examined in different sulphate solutions. Data show better strength achievement in cement mortars containing 10% MK than the OPC mortars alone.     

Partial replacement of metakaolin with red ceramic waste in geopolymer

Metakaolin was incrementally replaced (33.3%, 50% and 66.6%) by red ceramic waste in geopolymer formulation to study the effect on geopolymerisation and its resultant properties. The geopolymer binders composed of two calcined aluminosilicates (viz. Metakaolin and Red ceramic waste), NaOH and sodium silicate. In the experimental compositions, metakaolin was replaced gradually up to 66.6% in the clay fraction, the Si/Al increased from 3.36 to 5.16 and Na/Al increased from 0.93 to 1.38. The FTIR spectroscopic studies of geopolymer pastes along with XRD analysis indicated that the red ceramic waste partly reacts with alkali and takes part in geopolymer formation. Replacement of 33.3% metakaolin by the red ceramic waste in geopolymer binder did not reduce the compressive strength with respect to the pure metakaolin geopolymer here. Additional replacement resulted in a drastic decrease in the compressive strength of the geopolymer binder. However, the compressive strength of geopolymer mortars revealed interesting synergy between the amount of binder and particle packing in the mortar. Despite having a lower amount of binder phase, mortars with 33% and 50% red ceramic waste exhibited maximum compressive strength values. This has been attributed to improved particle packing through incorporation of red ceramic waste particles.     

Geopolymers based on a coarse low-purity kaolin mineral: Mechanical strength as a function of the chemical composition and temperature

A coarse mineral with 70% kaolinite and 30% quartz was calcined and chemically activated by alkaline solutions of Na₂SiO₃ and NaOH. The compressive strength evolution was investigated as a function of the curing temperature at 20 and 80 °C, and the molar ratios of SiO₂/Al₂O₃ (2.64-4.04) and Na₂O/Al₂O₃ (0.62-1.54). For curing at 20 °C, the best composition was SiO₂/Al₂O₃ = 2.96 and NaO/Al₂O₃ = 0.62, reaching 85 MPa at 28 days. Curing at 80 °C had a positive effect on the strength development only in the first 3 days. X-ray diffraction of the geopolymeric formulations showed the formation of amorphous silicoaluminates of similar nature. The microstructure consisted of unreacted quartz and metakaolinite particles in a matrix of silicoaluminate polymer and condensed silica gel from the unreacted sodium silicate.     

Multi-scale characteristics of magnesium potassium phosphate cement modified by metakaolin

Workability and early-ages mechanical properties are important indicators of magnesium potassium phosphate cement (MKPC) as a repair material. The effect of metakaolin (MK) on the setting time, fluidity and early-ages strength of MKPC paste was studied, and its influence mechanism was analyzed through pore structure, microstructure and nanomechanical properties. The results show that 10% and 20% of MK prolong the setting time of MKPC paste, but excessive MK shortens the setting time of MKPC paste. Meanwhile, incorporating MK reduces the fluidity of MKPC paste, and the early-ages strength of MKPC specimens increases when the substitution ratio of MK is 10%. When 10% of MK is incorporated to the MKPC paste, the 30-d shrinkage of the sample is only 69% of the control group. Meanwhile, a proper amount of MK can improve the pore structure of the MKPC specimen and make its microstructure denser by generating amorphous aluminosilicate phosphate gel. It is observed from the nano-scale characteristics that incorporating 10% MK can reduce the content of pore phase and unreacted MgO phase, and increase the volume fraction of hydration products.     

Geopolymers from Algerian metakaolin. Influence of secondary minerals

The influence of secondary phases (illite, quartz) on the geopolymerization reaction of metakaolin has been investigated by comparing two metakaolins, one prepared from a pure kaolinite and the other from illite- and quartz-containing Algerian kaolin from the Tamazert region, respectively. Geopolymerization was achieved by mixing the metakaolins with an alkaline sodium silicate solution at room temperature and curing at 50 °C. The products were characterized by X-ray diffraction and ²⁹Si and ²⁷Al MAS-NMR. The results show that the secondary phases, at the concentration used in this work, do not prevent the geopolymerization reaction.     

Comparative study on strength,sorptivity, and chloride ingress characteristics of air-cured and water-cured concretes modified with metakaolin

This paper reports an investigation in which the performance of plain and metakaolin (MK)-modified concretes were studied under two different curing regimes. The purpose of this study is to evaluate the effectiveness of MK in enhancing the strength and permeation properties of concrete. MK was used to replace 0–20% of Portland cement by weight in concrete with two water-binder (w/b) ratios of 0.35 and 0.55. The change in compressive strength, sorptivity, and chloride ingress with age at all cement replacement levels under both air and water curing are compared with those of the control concrete. The results indicated that the inclusion of MK greatly reduced sorptivity and chloride permeability of concrete in varying magnitudes, depending mainly on replacement level of MK, w/b ratio, curing condition, and chloride exposure period. It was found that under the inadequate or poor curing, MK-modified concretes suffered a more severe loss of compressive strength and permeability-related durability than the plain concretes.     

Resistance of blended cement pastes subjected to organic acids: Quantification of anhydrous and hydrated phases

Concrete for agricultural construction is often subject to aggressive environmental conditions. Ground granulated blast furnace slag (GGBFS) or metakaolin (MK) largely improve the chemical resistance of the binder. Anhydrous particles seem particularly resistant to the acid solution. The purpose of this study is to quantify anhydrous particles in blended cement pastes as a function of acid exposition time in order to evaluate their acid resistance.Cement pastes were moist cured for 28 days and then immersed in an acetic acid solution for 2 months. The quantification of the anhydrous phases was carried out using ²⁹Si MAS NMR, selective dissolution and back-scattered electron (BSE) images analysis, while the hydrated phases content was evaluated by TGA. After 28 days of hydration, 60% of OPC, 44% of GGBFS and 76% of MK particles were hydrated. The amount of anhydrous particles drops for all materials during acid immersion. After 2 months of immersion, the amount of anhydrous particles drops by 49%, 23% and 15% for OPC, GGBFS, and MK respectively. This study confirms that GGBFS and MK anhydrous and hydrates phases present higher acid resistance than OPC.