Mechanical/thermal dewatering of lignite. Part 3: Physical properties and pore structure of MTE product coals

The mechanical thermal dewatering (MTE) process has been shown to effectively dewater high moisture content low rank coals via the application of mechanical force at elevated temperatures.Using mercury intrusion porosimetry (MIP) as an investigative tool, this study examines how MTE processing conditions, such as temperature and pressure, affect the compressibility, pore size distribution, apparent (skeletal) density and shrinkage behaviour of three low rank coals sourced from Australia, Greece and Germany. As both pore filling and sample compression occurred at high mercury intrusion pressures, all MIP data were corrected for compression effects by using compressibility values derived from mercury extrusion data.The MTE process is shown to produce a low porosity coal, which, depending upon the processing conditions used, undergoes further shrinkage upon oven drying at 105 °C. An increase in MTE temperature (above about 85 °C) led to an increase in mesopore volume, which is caused by a hardening of the coal structure, leading to pore volume retention and a consequent reduction in percent shrinkage on oven drying. The increase in measured mesopore volume is also associated with an increase in measured surface area.The reverse trend is seen with increasing MTE pressure, where both the macro and mesopore volume decrease with pressure, causing the percent shrinkage to increase accordingly. This effect may be due to an increase in capillary forces caused by a decrease in the average pore diameter. The percent shrinkage increased up to a pore volume of about 0.1 cm³/g, beyond which no further reduction in pore volume was achieved. The decrease in mesopore volume is also associated with a decrease in measured surface area.Compressibility values derived from mercury extrusion data show that the MTE process has little impact on the network strength of the skeletal network structure of all three coals investigated. Likewise, the skeletal density remained relatively unchanged.The reduction in water content, pore volume and the changes in shrinkage behaviour under increasingly severe MTE conditions are suggestive of the physical changes that accompany increased coalification (rank) within the lignitic range.     

Microstructural and bulk property changes in hardened cement paste during the first drying process

This paper reports the microstructural changes and resultant bulk physical property changes in hardened cement paste (hcp) during the first desorption process. The microstructural changes and solid-phase changes were evaluated by water vapor sorption, nitrogen sorption, ultrasonic velocity, and ²⁹Si and ²⁷Al nuclear magnetic resonance. Strength, Young's modulus, and drying shrinkage were also examined. The first drying process increased the volume of macropores and decreased the volume of mesopores and interlayer spaces. Furthermore, in the first drying process globule clusters were interconnected. During the first desorption, the strength increased for samples cured at 100% to 90% RH, decreased for 90% to 40% RH, and increased again for 40% to 11% RH. This behavior is explained by both microstructural changes in hcp and C–S–H globule densification. The drying shrinkage strains during rapid drying and slow drying were compared and the effects of the microstructural changes and evaporation were separated.     

Prediction of self-desiccation in low water-to-cement ratio pastes based on pore structure evolution

High-performance concrete is sensitive to early-age cracking, mainly due to its rapidly-developing autogenous shrinkage. Autogenous shrinkage and internal relative humidity (RH) decrease are direct consequences of the emptying of capillary pores due to cement hydration in low water-to-cement ratio concretes. To predict early-age cracking, it is desirable to model the evolution of the internal RH, and the accompanying autogenous shrinkage, based on the microstructure evolution.In this paper, the pore size distribution of cement pastes measured by mercury intrusion porosimetry and the chemical shrinkage are used as input data for calculating the internal RH of Portland cement pastes with different water-to-cement ratios (0.30, 0.35 and 0.40). The composition of the extracted pore solution is also taken into account. The measured RH can be predicted with good accuracy (mostly within 1–2% RH). However, a number of sources of error both in the experiments and in the analysis need to be identified and controlled.     

Examining the relationship between the microstructure of calcium silicate hydrate and drying shrinkage of cement pastes

Cement paste undergoes a volumetric contraction called drying shrinkage when placed in a low relative humidity (RH) environment. Only a portion of this shrinkage is reversible upon rewetting. In order to understand better the mechanisms responsible for the irreversible portion of drying shrinkage, a quantitative comparison was made between shrinkage values and microstructural properties of cement pastes. Drying shrinkage, surface area and pore volume were manipulated using curing temperature and chemical admixtures. It was observed that total and irreversible drying shrinkage increase with surface area and pore volume as measured by nitrogen (1-40 nm pore radius range), when degree of hydration and water-to-cement ratio (w/c) are held constant (0.55 and 0.45, respectively).     

Eight-year exploration of shrinkage in high-performance concrete

In this paper, an experimental and analytical exploration on the effect of water-binder ratio (w/b), silica fume and age on autogenous, carbonation, drying and total shrinkage of high-performance concrete (HPC) is outlined. Eight types of HPC were studied. Carbonation, internal relative humidity (RH) and strength were studied on specimens from the same batch of HPC that was used in the studies of shrinkage. The results indicate fairly good correlation between carbonation, shrinkage, w/b and RH. The type and amount of silica fume affected shrinkage.     

掺加橡胶颗粒混凝土材料的性能研究

本文研究橡胶尺寸对橡胶水泥基材料性能的影响,选择三组粒径为6～8mm,3～5mm和0～2mm的橡胶代替骨料制备混凝土,研究制备混凝土材料的稠度和密度、孔径结构、机械强度和干燥收缩性能。结果表明,混凝土材料的稠度和密度随橡胶粒径的增加而降低;对于孔径结构来说,孔体积随着橡胶颗粒粒径尺寸的减小而增加,其中橡胶颗粒粒径尺寸对中孔(50 nm)体积的影响不如橡胶含量因素条件显著;混凝土材料的机械强度随着橡胶颗粒粒径的减小而降低;而混凝土材料干燥收缩率随着橡胶颗粒粒径的减小而增加。     

The shrinkage of alkali activated fly ash

In this study, the autogenous and drying shrinkage of alkali activated fly ash (AAFA) pastes prepared with different contents of sodium silicate solution are reported. A higher amount of both Na₂O and SiO₂ resulted in a larger autogenous and drying shrinkage. Although a large autogenous shrinkage was obtained during the first 1–3 days, cracking was not observed in the ellipse ring tests. In AAFA pastes, water was not a reactant, but mainly acted as a medium. The experiment results indicate that the autogenous shrinkage of AAFA is not caused by the well-known self-desiccation process that happened in cement paste, but related to the continuous reorganization and polymerization of the aluminosilicate gel structure. AAFA pastes with a larger drying shrinkage exhibited a higher weight loss. The different microstructures lead to the different drying shrinkage of these AAFA mixtures.     

Autogenous and drying shrinkage of alkali-activated slag mortars

Shrinkage of alkali-activated slag (AAS) cement is a critical issue for its industrial application. This study investigated the mechanisms and effectiveness of shrinkage-reducing agent (SRA) and magnesia expansive agent on reducing autogenous and drying shrinkage of AAS mortars that were activated by liquid sodium silicate (LSS) solution with modulus (SiO₂/Na₂O molar ratio) of 0-1.5. The results showed that the autogenous shrinkage of AAS mortars increased with the increase of LSS modulus from 0 to 0.5, then decreased as modulus increased up to 1.5. The drying shrinkage consistently increased with the increase in the modulus of LSS. The oxyalkylene alcohol-based SRA could significantly reduce the autogenous and drying shrinkage of AAS mortars while the magnesia expensive agent was comparatively less effective. The autogenous shrinkage of AAS mortars was inversely proportional to the internal relative humidity, while the drying shrinkage was more related to the mass loss of samples. Mathematical models were established to describe the autogenous and drying shrinkage behavior of AAS mortars.     

SAP内养护对碱激发矿渣胶凝材料性能的影响

碱激发矿渣(AAS)胶凝材料存在早期收缩大、开裂风险高的问题,限制了其工程应用。本文采用TAM、TGA、MIP等方法研究了高吸水性树脂(SAP)内养护对AAS胶凝材料水化热、水化产物及孔结构的影响,同时研究了SAP对AAS胶凝材料抗压强度及自收缩的影响规律。结果表明,SAP的加入会增加基体的孔隙率,降低AAS浆体的抗压强度,但是随着水化时间的延长,SAP的内养护作用可以促进矿渣水化,抗压强度的降低幅度逐渐减小。SAP的加入对AAS胶凝材料的水化放热过程有一定的延迟作用,表现为诱导期延长,第二放热峰滞后。SAP的加入使AAS胶凝材料水化产物总量增加,增加程度随着模数的增加而提高。此外,SAP抑制AAS浆体自收缩效果明显,添加SAP之后自收缩降低率最高可达81%。     

Na2SiO3/Na2CO3复合制备清洁型碱矿渣胶凝材料

为解决弱碱单独激发碱矿渣胶凝材料(AASM)时存在的力学性能弱、矿渣反应程度低等问题,缓解AASM的操作危害性,本文采用Na₂SiO₃/Na₂CO₃复合激发矿渣,研究了复合激发剂组成对AASM凝结时间、抗压强度、水化产物及自收缩的影响,并评估了AASM的环境效益。结果表明:随着Na₂CO₃碱当量的增加,AASM缓凝效果较为明显,抗压强度也有所降低,但抗压强度的降低幅度随龄期增大而减小。通过加入Na₂CO₃,AASM水化产物种类增多,C-(A)-S-H的峰值强度随Na₂CO₃碱当量占比的增加呈现出先增加后降低的趋势,因而解释了AASM浆体自收缩的变化。另外,由CO₂排放指数可以看出,Na₂SiO₃/Na₂CO₃复合激发矿渣较Na₂SiO₃单独激发更为清洁,环境效益显著。     

Interactions between shrinkage reducing admixtures (SRA) and cement paste's pore solution

Shrinkage reducing admixtures (SRA) have been developed to combat shrinkage cracking in concrete elements. While SRA has been shown to have significant benefits in reducing the magnitude of drying and autogenous shrinkage, it has been reported that SRA may cause a negative side effect as it reduces the rate of cement hydration and strength development in concrete. To examine the influence of SRA on cement hydration, this study explores the interactions between SRA and cement paste's pore solution. It is described that SRA is mainly composed of amphiphilic (i.e., surfactant) molecules that when added to an aqueous solution, accumulate at the solution-air interface and can significantly reduce the interfacial tension. However, these surfactants can also self-aggregate in the bulk solution (i.e., micellation) and this may limit the surface tension reduction capacity of SRA. In synthetic pore solutions, SRA is observed to form an oil-water-surfactant emulsion that may or may not be stable. Specifically, at concentrations above a critical threshold, the mixture of SRA and pore fluid is unstable and can separate into two distinct phases (an SRA-rich phase and an SRA-dilute phase). Further, chemical analysis of extracted pore solutions shows that addition of SRA to the mixing water depresses the dissolution of alkalis in the pore fluid. This results in a pore fluid with lower alkalinity which causes a reduction in the rate of cement hydration. This may explain why concrete containing SRA shows a delayed setting and a slower strength development.     

Experimental study on mechanism of autogenous shrinkage of concrete

It was proved that autogenous shrinkage of high-strength concrete could be almost the same as drying shrinkage. For cement paste with low water-cement ratio, shrinkage was observed even in water. Existing composite low evaluated well the restraining effect of aggregate on autogenous shrinkage. Moisture movement caused by capillary condensation was thought to be the cause of flexural strength reduction for sealed specimens.     

利用煅烧硅藻土制备高稳态超高性能混凝土基体研究

超高性能混凝土(UHPC)早期自收缩大,使结构存在收缩开裂风险,掺入天然多孔活性粉料以激发其火山灰和内养护协同效应可有效降低UHPC自收缩,改善基体体积稳定性。本文利用煅烧硅藻土以一定体积分数(3%、6%、9%)置换水泥制备UHPC基体,并对其新拌性能、力学性能、自收缩、耐久性能及孔结构与微观结构进行了系统评价。结果表明:掺入煅烧硅藻土能显著改善UHPC力学性能和体积稳定性,并进一步提升其耐久性能;掺入煅烧硅藻土UHPC基体孔结构得到优化,孔隙率降低,孔径细化;掺入煅烧硅藻土UHPC基体中C-S-H凝胶平均Ca/Si比下降,C-S-H(I)占比提高,水化产物结构及致密性改善。优化设计条件下,UHPC基体56 d抗压强度提高9%,56 d抗折强度提高18%,7 d自收缩下降29%,28 d快速氯离子迁移系数下降35%,28 d电通量下降27%。     

Relation between the molecular structure and the efficiency of superabsorbent polymers (SAP) as concrete admixture to mitigate autogenous shrinkage

Superabsorbent polymers (SAP) were studied as admixtures for mitigating the autogenous shrinkage of a high-strength concrete. The presence of Ca²⁺ ions in the alkaline solution modified the kinetics of the liquid uptake and release when compared to that in other saline solutions and distilled water. SAP with high density of anionic functional groups took up the cement pore solution quickly, but greatly released it subsequently. The cross-linking density had no pronounced influence on the behaviour of such SAP. SAP with lower density of anionic groups did not release the liquid over the time of experiment. All SAP counteracted autogenous shrinkage during the acceleration period of cement hydration. For the materials which released the absorbed pore solution no effect on autogenous shrinkage was found beyond the initial period. SAP materials which did not release the absorbed solution in the experiments with liquids continued the mitigation of autogenous shrinkage during the deceleration period. The internal curing had no negative effect on the compressive strength of the mortar.     

Requirements of organic gels for a successful ambient pressure drying preparation of carbon aerogels

In this paper, we investigated the requirements of organic gels for a successful ambient pressure drying by analyzing the role of the strength, the pore size and the surfactant of organic gels in decreasing the drying shrinkage of organic aerogels. Experimental results showed the effect of the decrease of the surface tension, resulting from the surfactant, on the drying shrinkage was very small and negligible. The drying shrinkage depended strongly on the strength and the pore size. Subsequently, the respective role of the strength and the pore size was evaluated. It can be found that the strength plays a greater role than the pore size.     

超细矿渣粉和偏高岭土对硫铝酸盐水泥早期收缩性能的影响

通过开展化学收缩、自收缩与干燥收缩试验,研究了超细矿渣粉和偏高岭土对硫铝酸盐水泥早期收缩性能的影响。结果表明,掺入超细矿渣粉与偏高岭土会增大水泥浆体的内部相对湿度,能有效抑制水泥浆体的化学收缩、自收缩与干燥收缩,且掺量越大,抑制效果越明显,根据水泥浆体的内部相对湿度能够大致判断其自收缩的变化规律。掺入超细矿渣粉与偏高岭土会加快硫铝酸盐水泥的早期水化,使化学收缩变化速率达到峰值的时间提前。当超细矿渣粉的掺量为20%(质量分数,下同)或偏高岭土的掺量为10%、20%时,与空白组相比水泥浆体的7 d自收缩分别减小了42.21%、35.89%和63.73%,7 d干燥收缩分别减小了24.89%、16.42%和30.87%。在相同掺量条件下,掺入偏高岭土的水泥浆体化学收缩、自收缩与干燥收缩显著小于掺入超细矿渣粉的水泥浆体。自收缩与线性化学收缩的比值随龄期的增长而减小,掺入超细矿渣粉与偏高岭土后,自收缩与线性化学收缩的比值进一步减小。     

硅灰和减缩剂对混凝土自收缩和孔隙的影响

硅灰和低水胶比会降低混凝土总孔隙率,但增加了混凝土自收缩,使其产生微裂纹。本文研究了掺入硅灰和减缩剂(SRA)对不同水胶比的混凝土自收缩和微观、宏观尺度孔径分布的影响。结果表明：掺入10%(体积分数)的硅灰会使混凝土自收缩增加27.3%～28.8%;而加入减缩剂使混凝土自收缩降低68.0%～85.1%,且对含有硅灰的混凝土样品降幅更大。此外,掺入硅灰和减缩剂可以使混凝土总孔隙率分别降低5.1%～6.0%和35.9%～39.7%,但硅灰会增大混凝土100 nm以下孔隙和100μm以上孔隙的体积占比,而减缩剂对这两类孔隙的体积则会起相反作用。同时,自收缩与100μm以上孔隙体积分数呈明显正相关关系。     

矿物掺和料与再生骨料对水泥强度和收缩性能的影响

矿物掺和料与再生骨料应用于水泥制品中是废弃物资源化利用的重要途径。为了研究矿物掺和料与再生骨料对水泥强度和收缩性能的影响,设计不同掺和料掺合比例与再生骨料取代率,进行不同龄期的强度、干燥收缩和早期自收缩测试。结果表明,粉煤灰降低水泥强度,而矿粉可提高水泥后期强度;粉煤灰和矿粉对水泥的干燥收缩有抑制作用,但对水泥早期自收缩有促进作用;再生骨料能够提高水泥强度,而对水泥的收缩性能无明显影响。     

Autogenous relative humidity change and autogenous shrinkage of high-performance cement pastes

In this paper, the effects of water to cementitious material ratio (w/cm), silica fume (SF) and ground blast-furnace slag (GBFS) on autogenous relative humidity (RH) change and autogenous shrinkage (AS) of high-performance cement pastes were studied. The mechanism of self-desiccation caused by mineral admixture and reduction of w/cm were studied by the parameters of mineral admixture self-desiccation-effect coefficient k and efficient w/cm r_e proposed. Furthermore, the relationship between autogenous RH and AS of high-performance paste was established. The results indicate that w/cm is a chief factor that affects autogenous RH change and AS of cement pastes. The lower the w/cm of paste is, the more reduction the autogenous RH and the increment of AS are. SF increases autogenous RH reduction and AS increment of cement paste at early ages, and GBFS increases autogenous RH reduction and AS increment at later ages. The effect of mineral admixtures on autogenous RH change of paste resulting from self-desiccation can be reflected effectively by the nonlinear equation with the parameters of k and r_e. There exists a good linear correlation between autogenous RH change and AS of cement pastes.     

Internal curing of engineered cementitious composites for prevention of early age autogenous shrinkage cracking

This investigation was carried out to study the effects of using a replacement percentage of saturated lightweight fine aggregate (LWA) as an internal curing agent on the shrinkage and mechanical behavior of Engineered Cementitious Composites (ECC). ECC is a micromechanically-based, designed high-performance, fiber-reinforced cementitious composite with high ductility and improved durability due to tight crack width. Standard ECC mixtures are typically produced with micro-silica sand (200 µm maximum aggregate size). Two replacement levels of silica sand with saturated LWA (fraction 0.59–4.76 mm) were adopted: the investigation used 10 and 20% by weight of total silica sand content, respectively. For each LWA replacement level, two different ECC mixtures with a fly ash-to-Portland cement ratio (FA/PC) of 1.2 and 2.2 were cast. In a control test series, two types of standard ECC mixtures with only silica sand were also studied. To investigate the effect of replacing a portion of the silica sand with saturated LWA on the mechanical properties of ECC, the study compared the results of uniaxial tensile, flexure and compressive strength tests, crack development, autogenous shrinkage and drying shrinkage. The test results showed that the autogenous shrinkage strains of the control ECCs with a low water-to-cementitious material ratio (W/CM) (0.27) and high volume FA developed rapidly, even at early ages. The results also showed that up to a 20% replacement of normal-weight silica sand with saturated LWA was very effective in reducing the autogenous shrinkage and drying shrinkage of ECC. On the other hand, the partial replacement of silica sand with saturated LWA with a nominal maximum aggregate size of 4.76 mm is shown to have a negative effect, especially on the ductility and strength properties of ECC. The test results also confirm that the autogenous shrinkage and drying shrinkage of ECC significantly decreases with increasing FA content. Moreover, increasing FA content is shown to have a positive effect on the ductility of ECC.