Effect of Curing Regime on Degree of Al^(3+) Substituting for Si^(4+) in C-S-H Gels of Hardened Portland Cement Pastes

The effect of curing regime on degree ofAl3＋ substituting for Si^4＋ （Al/Si ratio） in C-S-H gels of hardened Portland cement pastes was investigated by 29Si magic angel spinning （MAS） nuclear magnetic resonance （NMR） with deconvolution technique. The curing regimes included the constant temperature （20, 40, 60 and 80 ℃） and variable temperature （simulated internal temperature of mass concrete with 60 ℃ peak）. The results indicate that constant temperature of 20 ℃ is beneficial to substitution ofAl3＋ for Si4＋, and AI/Si ratio changes to be steady after 180 d. The increase of Al/Si ratio at 40 ℃is less than that at 20℃ for 28 d. The other three regimes of high temperature increase Al/Si ratio only before 3 d, on the contrary to that from 3 to 28 d. However, the 20 ℃ curing stage from 28 to 180 d at variable temperature regime, is beneficial to the increase of AI/Si ratio which is still lower than that at constant temperature regime of 20 ℃ for the same age. A nonlinear relation exists between the Al/Si ratio and temperature variation or mean chain length （MCL） of C-S-H gels, furthermore, the amount ofAl3＋ which can occupy the bridging tetrahedra sites in C-S-H structure is insufficient in hardened Portland cement pastes.

Early Stage Hydration Mechanism of Cellulose Ether Modified Thin Layer Cement Pastes

The early stage hydration mechanism of cellulose ether modified thin layer cement pastes was studied, using brick as the matrix. Samples of 6 h, 24 h, and 3 d and 7 d hydration time were analyzed to study the hydration law on the surface of high water-absorbing matrix. Hydration products were qualitatively and semi-quantitatively analyzed using XRD, TG-DSC-DTG, FTIR and SEM. The experimental results show that there is no enough water for 2 mm thick cement pastes to hydrate, because of rapid water absorption of matrix. Trace amounts of Ca （OH）2 was detected after three days hydration. With the prolongation of hydration time, the category and concentration of hydration products do not change. Compared with 2 mm thick cement pastes, 6 mm thick cement pastes and 10 mm thick cement pastes have lower dehydration rate and water loss. The humidity field of the cement paste show different changes within the same time. 6 mm thick cement paste and 10 mm thick cement pastes have longer time and more water to hydrate. Ca（OH）2 and ettringite were detected after 6 hours hydration and the concentrations of hydration products increased from 24 hours to 7 days.

Effect of Curing Regime on the Distribution of Al^(3+) Coordination in Hardened Cement Pastes

The effect of curing regime on the distribution ofAl3＋ coordination in hardened cement pastes within 28 d were investigated by 29Si and 27Al magic angle spinning （MAS） nuclear magnetic resonance（NMR） with deconvolution technique. The results indicate that the tetrahedral coordination Al3＋ incorporated in C-S-H structure mainly originate from the AP＋ incorporated in the alite and belite phases in the Portland cement. The curing regime of constant temperature of 20 ℃ is beneficial to the octahedral coordination Al3＋ transforming to tetrahedral coordination AP＋ incorporated in C-S-H structure. However, at curing regime of variable temperature, the temperature rising process is more advantageous to the transformation from ettringite to monosulphate, substitution of Al3＋ for Si4＋ in the C-S-H structure and the formation of the third aluminate hydrate （TAH） than that at constant temperature of 20 ℃. The high temperature of 60 ℃ in the holding temperature process promotes the decomposition of ettringite, and enhances the consumption of the Al3＋ incorporated in C-S-H phases and the Al3＋ in TAH for the monosulphate forming. The temperature decreasing promotes the transformation from monosulphate to ettringite, and increases the consumption of the Al3＋ incorporated in C-S-H phases, and then increases the quantity of the TAH.

Analysis of Air Voids Evolution in Cement Pastes Admixed with Non-ionic Cellulose Ethers

Four cellulose ethers（CEs） were compared for their effects on the pore structure of cement paste using mercury intrusion porosimetry. The experimental results show that the total pore volume and porosity of cement pastes containing the four cellulose ethers are significantly higher than that of the pure cement pastes and the total pore volume and porosity of cement pastes containing HEC（hydroxyethyl cellulose ether） or low viscosity cellulose ethers are low in four CEs. By changing the surface tension and viscosity of liquid phase and the strengthening of liquid film between air voids in cement pastes, CEs affect the formation, diameter evolution and upward movement of air voids and the pore structure of hardening cement paste. For the four CEs, the pore volume of cement pastes containing HEC or low viscosity cellulose ethers is higher with the diameter of 30-70 nm while lower with the diameter larger than 70 nm. CEs affect the pore structure of cement paste mainly through their effects on the evolvement of the small air voids into bigger ones when the pore diameter is below 70 nm and their effects on the entrainment and stabilization of air voids when the pore diameter is above 70 nm.

Hydration Heat Effect of Cement Pastes Modified with Hydroxypropyl Methyl Cellulose Ether and Expanded Perlite

Hydration heat effect of cement pastes and mechanism of hydroxypropyl methyl cellulose ether （HPMC） and expanded perlite in cement pastes were studied by means of hydration exothermic rate, hydration heat amount, FTIR and TG-DTG. The results show that HPMC can significantly delay the hydration induction period and acceleration period of cement pastes. As mixing amount increased, hydration induction period of cement pastes enlarged and accelerated period gradually went back. At the same time, the amount of hydration heat gradually decreased. Expanded perlite had worse delay effects and less change of hydration heat amount of cement pastes than HPMC. HPMC changed the structure of C-S-H during cement hydration. The more amount of HPMC, the more obvious effect. However, EXP had little influence on the structure of C-S-H. At the same age, the content of Ca （OH）2 in cement pastes gradually decreased as the mixing amount increase of HPMC and expanded perlite, and had better delay effect than that single-doped with HPMC or expanded perlite when HPMC and expanded nerlite were both dooed in cement pastes.

Adsorption and Desorption Characteristics of K^+ and Na^+ Ions in Fly Ash Blended Cement Pastes

Cement pastes containing 0%, 15%, 25% and 35% fly ash were prepared. After being cured for 90 days, all fly ash blended cement pastes were crushed and ground into powders with a particle size less than 80 μm and then the powders were immersed in alkali solutions. Adsorption characteristics of K^+ and Na^+ ions in the pastes were investigated. Meawhile, the desorption characteristics of the adsorbed alklai ions and the inherent K^+ and Na^+ ions in the pastes were also investigated. Results showed that the contents of K^+ and Na^+ ions adsorbed by the pastes increased with increasing the substitution levels of fly ash and/or the concentrations of alkali solutions. Each paste was characterized by having the same adsorption capacity for K^+ or Na^+ that was essentially independent of alkali concentration. Adsorption mechanism of K^+ and Na^+ ions by the pastes is believed to be an effect of charge compensation of the C-S-H gel. Adsorption-desorption of the adsorbed K^+ and Na^+ ions in the pastes is reversible. The inherent K^+ and Na^+ ions in the pastes entered rapidly into the de-ionized water during the first 120 minutes, and then they were released at a relatively slow rate. A steady-state alkali partition was reached at about 720 minutes. Some K^+ and Na^+ ions which were originally "bound" by the hydration products were considered to be released into de-ionized water. Leaching tests showed that there was no significant effect of fly ash on the retaining of available alkalis in the pastes. A part of the released alkali ions exists in the pore solutions and the other part may be physically adsorbed by the hydration products.

Influence of Polyepoxysuccinic Acid on Solid Phase Products in Portland Cement Pastes

The influence of polyepoxysuccinic acid（PESA）on the solid phase products in hydrated Portland cement pastes was investigated by isothermal calorimetry,X-ray diffraction（XRD）,^29Si and ^27Al nuclear magnetic resonance（NMR）.The results indicated that PESA bonds Ca^2＋ions in pore solution to prevent portlandite formation,and also combines with Ca^2＋ions on the surface of silicate minerals to prolong the control time of phase boundary reaction process,leading to the retardation of silicate mineral hydration.Meanwhile,the interlayer Ca^2＋ions in Jennite-like structure bridging PESA and C-S-H gels prevent silicate tetrahedron and aluminum tetrahedron from occupying the sites of bridging silicate tetrahedron,which causes the main existence of dimer in C-S-H structure,deceases the degree of Al^3＋substituting for Si^4＋and promotes the transformation from 4-coordination aluminum to 6-coordination aluminum.Furthermore,the-Ca^＋chelating group from reacting PESA with Ca^2＋ions combines easily with SO4^2-ions,resulting in transformation from ettringite,AFm to TAH（Third aluminum hydrate）.However,with the higher addition of PESA,it will bridge the excess PESA by Ca^2＋ions to form a new chelate with ladder-shaped double chains structure,which not only reduces the amount of PESA bonding Ca^2＋ions,but also decreases its solidifying capability for SO4^2-ions,leading to the transformation from TAH to AFm or ettringite.Meanwhile,at later hydration,the inhibition effect of PESA on cement hydration is weakened,and the transformation degree from TAH to AFm is higher than that to AFt with the addition of PESA.

Application of X-ray Computed Tomography in Characterization Microstructure Changes of Cement Pastes in Carbonation Process

The microstructure characteristics and meso-defect volume changes of hardened cement paste before and after carbonation were investigated by three-dimensional （3D） X-ray computed tomograpby （XCT）, where three types water-to-cement ratio of 0.53, 0.35 and 0.23 were considered. The high-resolution 3D images of microstructure and filtered defects were reconstructed by an XCT VG Studio MAX 2.0 software, The meso- defect volume fractions and size distribution were analyzed based on 3D images through add-on modules of 3D defect analysis. The 3D meso-defects volume fractions before carbonation were 0.79%, 0.38% and 0.05% corresponding to w/c ratio=0.53, 0.35 and 0.23, respectively. The 3D meso-defects volume fractions after carbonation were 2.44%, 0.91% and 0.14% corresponding to w/c ratio=0.53, 0.35 and 0.23, respectively. The experimental results suggest that 3D meso-defects volume fractions after carbonation for above three w/c ratio increased significantly. At the same time, meso-cracks distribution of the carbonation shrinkage and gray values changes of the different w/c ratio and carbonation reactions were also investigated.

Rheological Behaviors of Fresh Cement Pastes with Polycarboxylate Superplasticizer

The rheologicalbehaviors of fresh cement paste with polycarboxylate superplasticizer were systematically investigated.Influentialfactors including superplasticizer to cement ratio（Sp/C）,water to cement ratio（w/c）,temperature,and time were discussed.Fresh cement pastes with Sp/Cs in the range of 0 to 2.0% and varied W/Cs from 0.25 to 0.5 were prepared and tested at 0,20 and 40 °C,respectively.Flowability and rheologicaltests on cement pastes were conducted to characterize the development of the rheologicalbehavior of fresh cement pastes over time.The exprimentalresults indicate that the initialflowability and flowability retention over shelf time increase with the growth in superplasticizer dosage due to the plasticizing effect and retardation effect of superplasticizer.Higher temperature usually leads to a sharper drop in initialflowability and flowability retention.However,for the cement paste with high Sp/C or w/c,the flowability is slightly affected by temperature.Yield stress and plastic viscosity show similar variation trends to the flowability under the abovementioned influentialfactors at low Sp/C.In the case of high Sp/C,yield stress and plastic viscosity start to decline over shelf time and the decreasing rate descends at elevated temperature.Moreover,two equations to roughly predict yield stress and plastic viscosity of the fresh cement pastes incorporating Sp/C,w/c,temperature and time are developed on the basis of the existing models,in which experimentalconstants can be extracted from a database created by the rheologicaltest results.

Microstructural Evolution Mechanism of C-(A)-S-H Gel in Portland Cement Pastes Affected by Sulfate Ions

The microstructural evolution of C-（A）-S-H gel in Portland cement pastes immersed in pure water and 5.0 wt% Na2SO4 solution for different ages was comparatively investigated, by means of ^（29） Si NMR spectroscopy, and SEM-EDS analysis. Additionally, molecular dynamics simulation was performed to study the aluminum coordination status and interaction of sulfate ions in C-（A）-S-H gel. The results showed significant changes in the microstructural evolution of C-（A）-S-H gel in Portland cement paste. Sulfate attack has decalcifying and dealuminizing effect on C-（A）-S-H gel which is evident from increase in mean chain length（MCL） and decrease in Ca/Si ＆ Al[4]/Si ratios of C-（A）-S-H gel. Additionally, Molecular dynamics simulation proves that Al[4] substituted in silicate chains of C-（A）-S-H gel is thermodynamically metastable, which may explain its migration from the silicate chains and transformation to Al[6], thus lowering the Al[4]/Si ratio of C-（A）-S-H gel. SO4^（2-）ions can carry the interfacial Ca^（2＋） ions into the pore solution by the diffusion-absorption-desorption process, which unravels the mechanism of sulfate attack on C-（A）-S-H gel.

Using cemented paste backfill to tackle the phosphogypsum stockpile in China:A down-to-earth technology with new vitalities in pollutant retention and CO_(2) abatement

Phosphogypsum(PG),a hard-to-dissipate by-product of the phosphorus fertilizer production industry,places strain on the biogeochemical cycles and ecosystem functions of storage sites.This pervasive problem is already widespread worldwide and requires careful stewardship.In this study,we review the presence of potentially toxic elements(PTEs)in PG and describe their associations with soil properties,anthropogenic activities,and surrounding organisms.Then,we review different ex-/in-situ solutions for promoting the sustainable management of PG,with an emphasis on in-situ cemented paste backfill,which offers a cost-effective and highly scalable opportunity to advance the value-added recovery of PG.However,concerns related to the PTEs'retention capacity and long-term effectiveness limit the implementation of this strategy.Furthermore,given that the large-scale demand for ordinary Portland cement from this conventional option has resulted in significant CO_(2) emissions,the technology has recently undergone additional scrutiny to meet the climate mitigation ambition of the Paris Agreement and China's Carbon Neutrality Economy.Therefore,we discuss the ways by which we can integrate innovative strategies,including supplementary cementitious materials,alternative binder solutions,CO_(2) mineralization,CO_(2) curing,and optimization of the supply chain for the profitability and sustainability of PG remediation.However,to maximize the co-benefits in environmental,social,and economic,future research must bridge the gap between the feasibility of expanding these advanced pathways and the multidisciplinary needs.

INFLUENCE OF GLASS CULLET IN CEMENT PASTES

The present study investigates glass and cement compatibility with a view to use glass as a cement replacement. Amber, flint and green glasses were chosen due to their prevalence in the Greek market as packaging materials. The factors under investigation were the pozzolanicity of the glass cullet, the hydration rate and the mechanical strength development of the cement pastes, as well as the expansion of the specimens due to alkali-silica reaction. Moreover, the potential enhancement of glass pozzolanic activity was examined. The results of the study were encouraging to show the potentiality of utilising glass cullet in cementitious products.

Experimental research and numerical simulation of the multi-field performance of cemented paste backfill:Review and future perspectives

Cemented paste backfill(CPB)technology is a green mining method used to control underground goaves and tailings ponds.The curing process of CPB in the stope is the product of a thermo-hydro-mechanical-chemical multi-field performance interaction.At present,research on the multi-field performance of CPB mainly includes indoor similar simulation experiments,in-situ multi-field performance monitoring experiments,multi-field performance coupling model construction of CPB,and numerical simulation of the multi-field performance of CPB.Because it is hard to study the in-situ multi-field performance of CPB in the real stope,most current research on in-situ multi-field performance adopts the numerical simulation method.By simulating the conditions of CPB in the real stope(e.g.,maintenance environment,stope geometry,drainage conditions,and barricade and backfilling rates),the multi-field performance of CPB is further studied.This paper summarizes the mathematical models employed in the numerical simulation and lists the engineering application cases of numerical simulation in the in-situ multi-field performance of CPB.Finally,it proposes that the multi-field performance of CPB needs to strengthen the theoretical study of multi-field performance,form the strength design criterion based on the multi-field performance of CPB,perform a full-range numerical simulation of the multi-field performance of CPB,develop a pre-warning technology for the CPB safety of CPB,develop automatic and wireless sensors for the multi-field performance monitoring of CPB,and realize the application and popularization of CPB monitoring technology.

Rheological properties of a multiscale granular system during mixing of cemented paste backfill:A review

The technology of cemented paste backfill(CPB)is an effective method for green mining.In CPB,mixing is a vital process aiming to prepare a paste that meets the non-stratification,non-segregation,and non-bleeding requirements.As a multiscale granular system,homogenization is one of the challenges in the paste-mixing process.Due to the high shearing,high concentration,and multiscale characteristics,paste exhibits complex rheological properties in the mixing process.An overview of the mesomechanics and structural evolution is presented in this review.The effects of various influencing factors on the paste's rheological properties were investigated,and the rheological models of the paste were outlined from the macroscopic and mesoscopic levels.The results show that the mechanical effects and structural evolution are the fundamental factors affecting the rheological properties of the paste.Existing problems and future development trends are presented to change the practice where the CPB process comes first and the theory lags.

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.

Experimental study on thermal and mechanical properties of tailings-based cemented paste backfill with CaCl_(2)·6H_(2)O/expanded vermiculite shape stabilized phase change materials

CaCl_(2)·6H_(2)O/expanded vermiculite shape stabilized phase change materials(CEV)was prepared by atmospheric impregnation method.Using gold mine tailings as aggregate of cemented paste backfill(CPB)material,the CPB with CEV added was prepared,and the specific heat capacity,thermal conductivity,and uniaxial compressive strength(UCS)of CPB with different cement-tailing ratios and CEV addition ratios were tested,the influence of the above variables on the thermal and mechanical properties of CPB was analyzed.The results show that the maximum encapsulation capacity of expanded vermiculite for CaCl_(2)·6H_(2)O is about 60%,and the melting and solidification enthalpies of CEV can reach 98.87 J/g and 97.56 J/g,respectively.For the CPB without CEV,the specific heat capacity,thermal conductivity,and UCS decrease with the decrease of cement-tailing ratio.For the CPB with CEV added,with the increase of CEV addition ratio,the specific heat capacity increases significantly,and the sensible heat storage capacity and latent heat storage capacity can be increased by at least 10.74%and 218.97%respectively after adding 12%CEV.However,the addition of CEV leads to the increase of pores,and the thermal conductivity and UCS both decrease with the increase of CEV addition.When cement-tailing ratio is 1:8 and 6%,9%,and 12%of CEV are added,the 28-days UCS of CPB is less than 1 MPa.Considering the heat storage capacity and cost price of backfill,the recommended proportion scheme of CPB material presents cement-tailing ratio of 1:6 and 12%CEV,and the most recommended heat storage/release temperature cycle range of CPB with added CEV is from 20 to 40℃.This work can provide theoretical basis for the utilization of heat storage backfill in green mines.

Multiphysics processes in the interfacial transition zone of fiber-reinforced cementitious composites under induced curing pressure and implications for mine backfill materials: A critical review

The mesoscale fiber-matrix interfacial transition zone(FM-ITZ) under induced curing pressure plays a key role in the effectiveness of fiber reinforcement and the engineering application of fiber-reinforced cementitious composites(FRCCs). This critical review establishes the link among induced curing pressure(i.e., external loading condition), multiphysics processes(i.e., internal governing mechanism), and interface behavior(i.e., material behavior) for FRCC materials through analysis of the state-of-the-art research findings on the FM-ITZ of FRCC materials. The following results are obtained. For the mechanical process, the induced curing pressure changes the stress state and enhances multicracking behavior, which can strengthen the FM-ITZ. For the hydraulic process, the strengthened seepage of the FM-ITZ under induced curing pressure weakens the effective stress and exaggerates the deficiency in water retention capacity between the bulk matrix and the FMITZ. For the thermal process, the induced curing pressure causes a steep temperature gradient in the FM-ITZ and thus influences the temperature evolution and thermally-induced microcracks in the FM-ITZ. For the chemical process, the induced curing pressure enhances hydration kinetics and results in the formation of additional hydration products in the FM-ITZ. Moreover, recommendations are proposed on the basis of findings from this review to facilitate the implementation of fiber reinforcement in cemented paste backfill technology.

Early-Age Properties Development of Recycled Glass Powder Blended Cement Paste:Strengths,Shrinkage,Nanoscale Characteristics,and Environmental Analysis

Recycling solid waste in cement-based materials cannot only ease its load on the natural environment but also reduce the carbon emissions of building materials.This study aims to investigate the effect of recycled glass powder(RGP)on the early-age mechanical properties and autogenous shrinkage of cement pastes,where cement is replaced by 10%,20%and 30%of RGP.In addition,the microstructure and nano-mechanical properties of cement paste with different RGP content and water to binder(W/B)ratio were also evaluated using SEM,MIP and nanoindentation techniques.The results indicate that the early-age autogenous shrinkage decreases with the increase of RGP content and W/B ratio.While the mechanical strength deteriorates due to the addition of RGP,it can be compensated by reducing the W/B ratio.Although the addition of RGP increases the total porosity of the hardened paste,it reduces the small size porosity(<50 nm).In addition,the proportions of different types of C-S-H are changed,and the volume fraction of porosity is increased,but that of hydration products of cement paste is reduced due to the incorporation of RGP.Besides its pozzolanic activity,the mitigated shrinkage deformation that RGP is generating in cement pastes is encouraging for its use as a novel supplementary cementitious material that reduces the early-age cracking risk of cement-based materials.Meanwhile,the life cycle assessments indicate that the RGP-cement component is an economical and eco-friendly novel engineering material.

Experiment on acoustic emission response and damage evolution characteristics of polymer-modified cemented paste backfill under uniaxial compression

The mechanical properties of cemented paste backfill(CPB)determine its control effect on the goaf roof.In this study,the mechanical strength of polymer-modified cemented paste backfill(PCPB)samples was tested by uniaxial compression tests,and the failure characteristics of PCPB under the compression were analyzed.Besides,acoustic emission(AE)technology was used to monitor and record the cracking process of the PCPB sample with a curing age of 28 d,and two AE indexes(rise angle and average frequency)were used to classify the failure modes of samples under different loading processes.The results show that waterborne epoxy resin can significantly enhance the mechanical strength of PCPB samples(when the mass ratio of polymer to powder material is 0.30,the strength of PCPB samples with a curing age of 28 d is increased by 102.6%);with the increase of polymer content,the mechanical strength of PCPB samples is improved significantly in the early and middle period of curing.Under uniaxial load,the macro cracks of PCPB samples are mostly generated along the axial direction,the main crack runs through the sample,and a large number of small cracks are distributed around the main crack.The AE response of PCPB samples during the whole loading process can be divided into four periods:quiet period,slow growth period,rapid growth period,and remission period,corresponding to the micro-pore compaction stage,elastic deformation stage,plastic deformation stage,and failure instability stage of the stress-strain curve.The AE events are mainly concentrated in the plastic deformation stage;both shear failure and tensile failure occur in the above four stages,while tensile failure is dominant for PCPB samples.This study provides a reference for the safety of coal pillar recovery in pillar goaf.

Effect of Hydrated Calcium Aluminate Cement on the Chloride Immobilization of Portland Cement Paste

To improve the efficiency and stability of chloride immobilization of portland cement paste,hydrated calcium aluminate cement(HCAC)prepared by wet grinding of CAC was added into portland cement paste as an additive.The immobilized chloride ratio(ICR)was evaluated,and the mechanism of chloride immobilization was researched by XRD,DTG,NMR,and MIP tests.The analysis results demonstrated that HCAC could improve the chloride immobilization capacity of portland cement paste.The mechanism was attributed to the following aspects:chemical binding capacity was enhanced via producing more Kuzel’s salt;physical adsorption capacity was reduced by decreasing the C-S-H gel;migration resistance was enhanced through refining the pore structure.