Investigation on the Thermo-dynamics of Alkali-activated Carbonatite

The thermo-dynamics of reactions between carbonatite and sodium silicate solution at ordinary temperature （25℃） were investigated. The calculated results indicate that at ordinary temperature, the reactions between dolomite, calcite, Ca2＋ and Mg2＋ in carbonatite and H4SiO4, tl3SiO4- and H2SiO42- in sodium silicate solution to form the cementitious products of hydrated calcium silicate or hydrated magnesium silicate all possibly happen; among these reactions, the reactions to form gyrolite （2CaO.3SiO2.2.5H2O） and serpentine （3MgO.2SiO2-2H20） are the most possible to occur. Further, the dissociation degree of dolomite and calcite and the activity of H3SiO4 , H2SiO42- and H4SiO4 ions are the key factors to influence the reactions.

Setting and Strength Characteristics of Alkali-activated Carbonatite Cementitious Materials with Ground Slag Replacement

The effect of the ground granulated blast-furnace slag （ GGBFS ） addition, the modulus n （ mole rutio of SiO2 to Na2O ） and the concentrution of sodium silicate solution on the compressive strength of the material, i e alkuli-activated carbonatite cemeutitious material （ AACCM for short ） was investiguted. In addition, it is found that barium chloride has a sutisfiwtory retarding effect on the setting of AACCM in which more than 20% （ by mass ） ground carbonatite was replaced by GGBFS. As a result, a cementitious material, in which ground carbonatite rock served as dominative starting material, with 3-day and 28-day compressive strength greuter them 30 MPa and 60 MPa and with continuous strength gain beyond 90 days was obtained.

Fundamental Study on Alkali-Activated Slag System with Sodium Carbonate or Calcium Hydroxide

Cement as a building material, has high fluidity, compressive strength, and durability, but carbon dioxide emissions during cement production are a major problem. As one of the countermeasures, alkali-activated cement using blast furnace slag powder with alkaline stimulants is considered to be a very promising solution for reducing carbon dioxide emissions, but there is a lack of information about the fundamental properties of alkali-activated materials. This study presents an experimental investigation of the fundamental properties of an alkali-activated slag system with sodium carbonate (NC) and calcium hydroxide (CH). The effects of calcium sulfo-aluminate (CSA) and shrinkage reducing agent (SRA) on the properties of blast furnace slag (BFS) based alkali-activated mixture were also investigated. In the experiments, fundamental characteristics including compressive strength, drying shrinkage, and water penetration tests of mortar were evaluated. Porosity, pH, and ignition loss were measured to verify the effectiveness of the materials. The experimental investigation revealed that the compressive strength was increased with the increasing replacement rates of NC in the BFS mortar, and in the case of water to BFS ratio of 0.45 with sodium carbonation addition contents 10 wt.%, the compressive strength for 28 days of curing reaches more than 50 MPa. Low water to BFS ratio and higher addition ratio of NC had a positive effect on the compressive strength development of mortar. Incorporating NC into BFS would affect the decrease in porosity and increase in ignition loss, leading to higher compressive strength. There was a negligible change to the compressive strength, porosity, pH, and ignition loss of BFS samples made with CH, thus, the addition rates of CH to BFS have no or little significant effect on the fundamental properties of alkali-activated cement. From the results of drying shrinkage and water penetration tests, the addition of NC and CH only to BFS exhibited poor drying shrinkage and water penetration characteristics. However, these problems may be overcome due to the use of CSA or SRA in the alkali-activated system made with NC or CH.

Hydration Characteristics and Microstructure of Alkali-Activated Slag Concrete: A Review

Alkali-activated slag concrete (AASC) is a new green building material. The amount of CO_(2) produced by AASC is 1/5th of that produced by ordinary Portland cement concrete (OPCC). In addition, AASC promotes the reuse of slag and other wastes and saves resources. Furthermore, the scope of use of slag has been expanded. The progress of the research on the hydration characteristics, microstructure, interfacial transition zone, and pore structure of AASC based on the relevant literatures was analyzed and summarized in this study. The influences of the slag composition, the type and dosage of the alkali activator, and the curing conditions on the hydration characteristics and the microstructure of the AASC were discussed. Relatively few research results on the microstructure of AASC are available, and the relevant conclusions are not completely consistent. Moreover, there are many constraints on the development of AASC (e.g., complex composition of raw materials of slag, large shrinkage deformation, and low fluidity). Therefore, further research is required.

A machine learning model to predict unconfined compressive strength of alkali-activated slag-based cemented paste backfill

The unconfined compressive strength(UCS)of alkali-activated slag(AAS)-based cemented paste backfill(CPB)is influenced by multiple design parameters.However,the experimental methods are limited to understanding the relationships between a single design parameter and the UCS,independently of each other.Although machine learning(ML)methods have proven efficient in understanding relationships between multiple parameters and the UCS of ordinary Portland cement(OPC)-based CPB,there is a lack of ML research on AAS-based CPB.In this study,two ensemble ML methods,comprising gradient boosting regression(GBR)and random forest(RF),were built on a dataset collected from literature alongside two other single ML methods,support vector regression(SVR)and artificial neural network(ANN).The results revealed that the ensemble learning methods outperformed the single learning methods in predicting the UCS of AAS-based CPB.Relative importance analysis based on the bestperforming model(GBR)indicated that curing time and water-to-binder ratio were the most critical input parameters in the model.Finally,the GBR model with the highest accuracy was proposed for the UCS predictions of AAS-based CPB.

Geology and mineralization of the Bayan Obo supergiant carbonatite-type REE-Nb-Fe deposit in Inner Mongolia, China: A review

The Bayan Obo supergiant carbonatite-related rare-earth-element-niobium-iron(REE-Nb-Fe) endogenetic deposit(thereafter as the Bayan Obo deposit), located at 150 km north of Baotou City in the Inner Mongolia Autonomous Region, is the largest rare-earth element(REE) resource in the world. Tectonically,this deposit is situated on the northern margin of the North China Craton and adjacent to the Xing’anMongolian orogenic belt to the south. The main strata within the mining area include the Neoarchean Se’ertengshan Group and the Mesoproterozoic Bayan Obo Group. Generally, the rare earth, niobium, and iron mineralization within the deposit are intrinsically related to the dolomite carbonatites and the extensive alteration of the country rocks caused by the carbonatite magma intrusion. The alteration of country rocks can be categorized into three types: contact metasomatism(anti-skarn and skarn alteration), fenitization,and hornfelsic alternation. As indicated by previous studies and summarized in this review, the multielement mineralization at Bayan Obo is closely associated with the metasomatic replacement of siliceous country rocks by carbonatite magmatic-hydrothermal fluids. The metasomatic process is comparable to the conventional skarnification that formed due to the intrusion of intermediate-acid magmatic rocks into limestone strata. However, the migration pattern of Si O2, Ca O, and Mg O in this novel metasomatic process is opposite to the skarn alteration. Accordingly, this review delineates, for the first time, an antiskarn metallogenic model for the Bayan Obo deposit, revealing the enigmatic relationship between the carbonatite magmatic-hydrothermal processes and the related iron and rare earth mineralization.Moreover, this study also contributes to a better understanding of the REE-Nd-Fe metallogenetic processes and the related fluorite mineralization at the Bayan Obo deposit.

Efficient Use of Steel Slag in Alkali-Activated Blast Furnace Slag Based Geopolymer

Energy shortage and the emission of greenhouse gases have become a global problem of urgent concern.Therefore,there is an urgent need to develop a low carbon building material.Geopolymers have become a hot topic due to their environmental sustainability and the feasibility of immobilizing industrial waste.In this paper,steel slag(SS)fines were investigated as auxiliary materials of blast furnace slag(BFS)based geopolymer.The hydration heat properties,flowability,compressive strength,sorptivity coefficient,X-ray diffraction(XRD),and scanning electron microscopy(SEM)of the geopolymer pastes were determined.The results showed that the incorporation of SS weakened the reactivity of the BFS-based geopolymer paste and improved the flow values of the paste.The compressive strength of the geopolymer with 20%SS content reached 117 MPa at 28 d.The geopolymer specimens with high compressive strength showed a low sorptivity coefficient.The microscopic results showed that the addition of the appropriate amount of SS reduced the cracks,improved the density of the geopolymer,and produced a geopolymer composite with excellent mechanical properties.

Distribution of Na+and Mechanical Properties of Hardened Body of Alkali-activated Cementitious Materials

To explore the distribution of and the mechanical properties(compressive strength)of the hardened body of alkali slag-fly ash cementitious materials,this study was conducted by using the XRD,FTIR,SEM/EDS,and other test methods in three conditions:airtight drying(AD),airtight immersion(AI),and airtight soaking(AS).The 1D distribution law of free of hardened body under standard curing conditions was explored.The experimental results show that under standard curing conditions,the 1D distribution of within 0d-3 d shows a∨-shaped distribution,within 3-7 d show a∧-shaped distribution,and within 7-28 d tends to be balanced.The test results of leaching rate show that the free was the most stable under AD conditions and the hardened body bound the most by XRD,FTIR and SEM/EDS.And the compressive strength of the hardened body was the highest.The compressive strength of 28th reached 95.9 MPa.The definite distribution of provides an important reference for the strength development and durability evaluation of the hardened body of alkaliexcited cementitious materials.

Influence of Erosion Induced by NaCl on the Mechanical Performances of Alkali-Activated Mineral Admixtures

In this paper,the influence of NaCl freeze-thaw(F-T)cycles and dry-wet(D-W)alternations on theflexural,com-pressive and bonding strengths of alkali-activatedfly ash(FA)and a blast furnace slag powder(BFS)is investi-gated.The considered NaCl concentration is 3%.The effect of polypropylenefibers on the mechanical strengths is also examined.Scanning electron microscopy(SEM),thermogravimetry(TG)and X-ray diffraction(XRD)are selected to discern the mechanisms underpinning the NaCl-induced erosion.The obtained results indicate that the best results in terms of material resistance are obtained with admixtures containing 60%BFS and 40%FA in terms of mass ratio and 3%polypropylenefibers in terms of volume ratio.The maximum rates of decrease of theflexural,compressive and bonding strengths after 300 NaCl F-T cycles are 21.5%,20.3%and 22.6%,respec-tively.The corresponding rates of decrease due to NaCl D-W alternations are 28.1%,26.1%and 31.5%,respec-tively.The TG curves show that the alkali-activating activity of BFS is higher than that of FA.Moreover,in thefirst case,the microstructure of the hydration products is more compact.The results also show that NaCl F-T cycles lead to increasing cracks in the alkali-activated BFS.

Carbonatite Occurrence in Ambaji-Sendra Belt of NW Indian Shield: Evidence of Carbonatitic Magmatism in the Subduction Setting

The paper represents a new discovery of a late Mesoproterozoic lenticular and discontinuous, carbonatitic body exposed at Basantgarh, Sendra and near the Abu-road area of the Ambaji-Sendra belt of the South Delhi Fold Belt. It is medium to coarse-grained and light to dark coloured compact rock. The common associates of the carbonatitic rock are felsic rocks, rich in alkalies. Carbonatite contains more than 50% carbonate minerals, the majority of which are calcite, dolomite, ankerite, augite-aegirine augite and plagioclase. It is classified as calcite carbonatite of the sövite variety due to its coarse-grained character, chemically as calico-carbonatite and magnesio-carbonatite and even as silico-carbonatites for having more than 20% SiO2. The ∑REE contents of calico-carbonatite samples are nearly 100 times greater than magnesio-carbonatite. Chondrite normalised REE profiles of calcio-carbonatites are LREE enriched with nearly flat HREEs whereas the magnesio-carbonatite is characterised by flat REE patterns. The mantle-normalized incompatible trace element spidergram of Ambaji-Sendra belt carbonatites shows distinct negative anomalies of Ba, Nb, Ta, P, Sm, Eu, Ti and Y and positive at U and Pb by calcio-carbonatite whereas the magnesio-carbonatite displays negative kinks at K, Zr, Nb, Ta and Ti and positive at Th, Pb and Sr. The variable and/or contrasting enrichment/depletion in various elements in the two types of Ambaji-Sendra belt carbonatite is attributed either to significant differences in the type and modal proportion of different accessory mineral species or selective incorporation of metasomatic fluids during the subduction process. The chemical attributes of Ambaji-Sendra belt carbonatite suggest its emplacement in subduction settings.

Carbonatites in China:A review for genesis and mineralization

Carbonatites are commonly related to the accumulation of economically valuable substances such as REE, Cu, and P. The debate over the origin of carbonatites and their relationship to associated silicate rocks has been ongoing for about 45 years, Worldwide, the rocks characteristically display more geochemical enrichments in Ba, Sr and REE than sedimentary carbonate rocks. However, carbonatite＇s geochemical features are disputed because of secondary mineral effects. Rock-forming carbonates from carbonatites at Qinling, Panxi region, and Bayan Obo in China show REE distribution patterns ranging from LREE enrichment to flat patterns. They are characterized by a Sr content more than 10 times higher than that of secondary carbonates. The coarse- and fine-grained dolomites from Bayan Obo H8 dolomite marbles also show similar high Sr abundance, indicating that they are of igneous origin. Some carbonates in Chinese carbonatites show REE （especially HREE） contents and distribution patterns similar to those of the whole rocks. These intrusive carbonatites display lower platinum group elements and stronger fractionation between Pt and lr relative to high-Si extrusive carbonatite. This indicates that most intrusive carbonatites may be carbonate cumulates. Maoniuping and Daluxiang in Panxi region are large REE deposits. Hydrothermal fluorite ore veins occur outside of the carbonatite bodies and are emplaced in wallrock syenite. The fluorite in Maoniuping has Sr and Nd isotopes similar to carbonatite. The Daluxiang fluorite shows Sr and REE compositions different from those in Maoniuping. The difference is reflected by both the carbonatites and rock-forming carbonates, indicating that REE mineralization is related to carbonatites. The cumulate processes of carbonate minerals make fractionated fluids rich in volatiles and LREE as a result of low partition coefficients for REE between carbonate and carbonatite melt and an increase from LREE to HREE. The carbonatite-derived fluid has interacted with wallrock to form REE ore veins. The amount of carbonatite dykes occurring near the Bayan Obo orebodies may support the same mineralization model, i.e. that fluids evolved from the carbonatite dykes reacted with H8 dolomite marble, and thus the different REE and isotope compositions of coarse- and fine-grained dolomite may be related to reaction processes.

Geochronology and mineralogy of the Weishan carbonatite in Shandong province, eastern China

The Weishan REE deposit is located at the eastern part of North China Craton(NCC), western Shandong Province. The REE-bearing carbonatite occur as veins associated with aegirine syenite. LA-ICP-MS bastnaesite Th-Pb ages(129 Ma) of the Weishan carbonatite show that the carbonatite formed contemporary with the aegirine syenite. Based on the petrographic and geochemical characteristics of calcite, the REEbearing carbonatite mainly consists of Generation-1 igneous calcite(G-1 calcite) with a small amount of Generation-2 hydrothermal calcite(G-2 calcite). Furthermore, the Weishan apatite is characterized by high Sr, LREE and low Y contents, and the carbonatite is rich in Sr, Ba and LREE contents. The δ^(13)Cv-PDB(-6.5‰ to -7.9‰) and δ^(13)OV-SMOW(8.48‰-9.67‰) values are similar to those of primary, mantlederived carbonatites. The above research supports that the carbonatite of the Weishan REE deposit is igneous carbonatite. Besides, the high Sr/Y, Th/U, Sr and Ba of the apatite indicate that the magma source of the Weishan REE deposit was enriched lithospheric mantle, which have suffered the fluid metasomatism. Taken together with the Mesozoic tectono-magmatic activities, the NW and NWW subduction of Izanagi plate along with lithosphere delamination and thinning of the North China plate support the formation of the Weishan REE deposit. Accordingly, the mineralization model of the Weishan REE deposit was concluded: The spatial-temporal relationships coupled with rare and trace element characteristics for both carbonatite and syenite suggest that the carbonatite melt was separated from the CO_2-rich silicate melt by liquid immiscibility. The G-1 calcites were crystallized from the carbonatite melt, which made the residual melt rich in rare earth elements. Due to the common origin of G-1 and G-2 calcites, the REE-rich magmatic hydrothermal was subsequently separated from the melt. After that, large numbers of rare earth minerals were produced from the magmatic hydrothermal stage.

Bayan Obo Carbonatites:Texture Evidence from Polyphase Intrusive and Extrusive Carbonatites

Most of the so-called Bayan Obo fine-grained dolomite marbles collected from the main and east orebodies show a microporphyritic texture,namely the microphenocrysts are set in a very finegrained matrix,although nearly all of them have undergone recrystallization caused either by deformation or alteration.The texture seems likely to have maintained the original features.It is known that one of the most characteristic textures of volcanic rocks is the porphyritic texture,and the microporphyritic texture is a variety in which both the phenocrysts and the matrix are only distinguishable with the microscope.Therefore,the dolomite marbles in the main and east orebodies may be related to the extrusive carbonatites.In addition,there also occur some carbonatite sills and dykes with different textures at Bayan Obo.Thus,the Bayan Obo carbonatites are polyphase intrusive and extrusive carbonatites.

The Durability of Alkali-Activated Materials in Comparison with Ordinary Portland Cements and Concretes:A Review

China is the largest producer and user of ordinary Portland cement(OPC),and the rapid growth of infrastructure development demands more sustainable building materials for concrete structures.Alkali-activated materials(AAMs)are a new type of energy-saving and environmentally friendly building material with a wide range of potential applications.This paper compares the durability of AAMs and 0 PC-based materials un der sulfate attack,acid corrosion,carb on ation,and chloride penetratio n.Different AAMs have shown distinct durability properties due to different compositions being formed when different raw materials are used.According to the calcium(Ca)concentration of the raw materials,this paper interprets the deterioration mechanisms of three categories of AAMs:calcium-free,low-calcium,and calcium-rich.Conflicts found in the most recent research are highlighted,as they raise concerns regarding the consistenee and long-term properties of AAMs.Nevertheless,AAMs show better durability performances than OPC-based materials in general.

Fenitized Wall Rock Geochemistry of the First Carbonatite Dyke at Bayan Obo, Inner Mongolia, China

The first carbonatite dyke at Bayan Obo is well exposed on the surface for a length and width of approximately 60 m and 1.1-1.5 m, respectively. Along its strike, the fenitized H1 （Qs） and H2 （Cs） quartzite is replaced by Na-amphiboles, aegirines, and alkali-feldspars, intermittently stretching as far away as 800 m in length. Based on petrographical characteristics, the dyke＇s fenitized wall rocks are divisible into different zones： （1） outer, （2） middle, and （3） inner. The outer zone is 5-17 m from the NW margin of the dyke. The middle zone is located at 3.5-5 m from the NW margin of the dyke. The inner contact zone is located between direct contact with the dyke and 3.5 m from the dyke. In the outer zone, upon visual examination, no evidence of outcrop fenitization was found and the major elemental rock composition is nearly identical to the unaltered H1 and H2 lithologies. In the thin sections, however, small amounts of Na-amphibole and phlogopite are present. Despite relatively poor development throughout the 5 m of fenitization, the wall rocks have retained at least a small geochemical signature comparable to the original sedimentary protolith. The fenites occurring in the inner zone exhibit distinct variations, not only for the sharp contact at the outcrop scale, but also for variations in major, rare earth elements （REE）, and trace elements and Sm-Nd isotope composition. The wall rocks within 3.5 m have undergone strong fenitization, inheriting the geochemical signature derived from the carbonatite dyke. Fenitization in the middle zone was not as strong, at least compared to the inner zone, but was stronger than the outer zone. Compared to some trace elements and REEs, the major elements are relatively immobile during fenitization. The Sm-Nd isotope data for the carbonatite dyke and the adjacent fenitized wall rocks, where the Sm and Nd originate solely from the dyke, plots as a six-point isochron with an age of 1308~56 Ma. This age is identical to that of ore-bearing dolomite carbonatite and the related ore-forming events, indicating that there may be a petrogenetic link between the two. Based on Sr and Nd isotope compositional data, the first carbonatite dyke may be derived from an enriched mantle.

Magnesia Modification of Alkali-Activated Slag Fly Ash Cement

A new type of magnesia modification alkali-activated cement was prepared, the strength, setting time, shrinkage ratio and cracking behavior, as well as the composition and structure of the hydration product were investigated. The results indicate that the setting time of this cement is similar to that of the ordinary commercial cements; its strength reaches the standard of 42.5 degree cement, its cracking resistance has been remarkably improved because of the micro-aggregate effect of fly ash and shrinkage compensating of magnesia.

Development of Cementitious Materials Utilizing Alkali-activated Yellow River Silt

The possibility of preparing cementitious materials by the alkali-activated method using Yellow River sediment(The second largest river in China)as raw material and the modification effect on different slag addition were investigated.Sodium silicate and calcium hydroxide were used as the activator,and the specimens were prepared by the press molding method.The hydration process,hydration products,pore characteristics,and mechanical properties were investigated using SEM/EDS,FTIR,TG/DTG,XRD,MIP,and uniaxial compressive strength experiments,respectively.The results showed that the compressive strength of the modified yellow river silt-based cementitious material was significantly increased when the water glass dosage was 12 wt%(Ms=1.8)and the slag dosage was 40%,and its 90-day maximum compressive strength could reach 53 MPa.

A Geochemical Study of an REE-rich Carbonatite Dyke at Bayan Obo,Inner Mongolia,Northern China

An REE-rich carbonatite dyke was found in Dulahala, close to the Bayan Obo superlarge REE-Nb-Fe mineral deposit in Inner Mongolia, northern China. The REE content in the dyke varies greatly, from 1% up to 20% (wt), which might constitute rich REE ores. Light REEs in the carbonatite are enriched and highly fractionated relative to heavy REEs and there is no Eu anomaly. The REE and trace element distribution patterns of the carbonatite are identical to those of fine-grained dolomite marble which is the host rock of the Bayan Obo REE-Nb-Fe superlarge mineral deposit. This indicates a petrogenetic linkage between the REE-rich carbonatite and the mineralizations in this region.

Effect of activator on rheological properties of alkali-activated slag-fly ash pastes

The time-dependent rheological behaviors of alkali-activated cement(AAC)are expected to be precisely controlled,in order to meet the requirements of modern engineering practices.In this paper,the effects of activator,including the Na_(2)O concentration and SiO_(2)/Na_(2)O(S/N)molar ratio,on the rheological behavior of alkali-activated slag fly ash pastes were investigated.The small amplitude oscillatory shear(SAOS)and shear test were used to evaluate the structural build-up and flowability of pastes.Besides,zeta potential measurement,calorimetric test and thermogravimetric analysis(TGA)were carried out to reveal the physico-chemical mechanisms behind the rheological evolution of fresh pastes.It was found that high Na_(2)O concentration and low S/N molar ratio improved the flowability and structural build-up rate of paste.Moreover,the structural build-up of alkali-activated slag-fly ash pastes consists of two stages,which is controlled by the dissolution of solid reactants and formation of C-(A)-S-H gels,respectively.

Geochemical Characteristics of a Carbonatite Dyke Rich in Rare Earths from Bayan Obo, China

The whole-rock geochemistry of a rare earths rich carbonatite dykes that locates at Dulahala and lies 3 km north-east to the East Ore body of the giant Bayan Obo RE-Nb-Fe deposit was analysed. The dyke cuts cross H1 coarse quartz sandstone and H2 fine quartzite of the Proterozoic Bayan Obo group. RE content in the dyke varies greatly up to 20% (mass fraction), which comprises rich RE ores. Light RE in carbonatites are extremely enriched and strongly fractionated relative to heavy RE, but no Eu anomaly. The carbonatite may be produced by mechanisms as follows: the carbonatite mana is directly formed by very low degree (F <1%) partial melting of enriched lithospheric mantle, leaving residual minerals characterized by abundant garnet; then the magma arises into a chamber within the crust where they will undergo fractional crystallization, which makes RE further concentrated in carbonatite. The RE patterns and spider diagrams of the carbonatite are identical to those fine-grained dolomite marble that is the ore-host rock for the Bayan Obo deposit. However, the carbonatite is calcic, which is different from the fine-grained dolomite marble in major element geochemistry. The difference is suggested to be resulted from that the carbonatite dyke is not affected by a large scale dolomitization, while the fine-grained dolomite marble might be the product of dolomitized carbonatite intrusive body that might set up a hydrothermal system in the region, which transported Mg from the Bayan Obo sediments, especially form the shales to the carbonatite intrusion.