Early hydration and setting of Portland cement monitored by IR, SEM and Vicat techniques

Diffuse Reflectance Infrared DR-FTIR spectroscopy is employed to monitor chemical transformations in pastes of Portland limestone cement. To obtain a sufficient time resolution a freeze-dry procedure is used to instantaneously ceasing the hydration process. Rapid re-crystallization of sulphates is observed during the first 15 s, and appears to be complete after ~ 30 min. After ~ 60 min, spectroscopic signatures of polymerizing silica start to emerge. A hump at 970-1100 cm^− 1 in conjunction with increasing intensity in the water bending mode region at 1500-1700 cm^− 1 is indicative of the formation of Calcium Silicate Hydrate, C-S-H. Simultaneously with the development of the C-S-H signatures, a dip feature develops at 800-970 cm^− 1, reflecting the dissolution of Alite, C₃S. Setting times, 180 (initial) and 240 (final) minutes, are determined by the Vicat technique. Combining DR-FTIR, SEM and Vicat measurements it is concluded that the setting is caused by inter-particle coalescence of C-S-H.     

不同稳泡剂对发泡水泥性能的影响

以普通425水泥为胶凝材料,分别以硬脂酸、司班80、十二烷基磺酸钠为稳泡剂,并添加多种外加剂制备发泡水泥保温材料,探讨三种稳泡剂对发泡水泥的泡孔结构、干密度、吸水率以及抗折强度、抗压强度等性能的影响。结果表明,采用司班80为稳泡剂制备的发泡水泥泡沫稳定性好、泡孔密集且均一,吸水率低、力学强度最佳,综合性能最优。硬脂酸为稳泡剂制备的发泡水泥性能次之,十二烷基磺酸钠为稳泡剂制备的发泡水泥性能最差。     

Effect of different foam stabilizers on the setting behavior and pore characteristics of CAC-bonded Al2O3 foamed ceramics

Calcium aluminate cement (CAC) was used in this work as a novel binder of the foam slurries to prepare Al₂O₃ foamed ceramics. The different foam stabilizers employed in the slurries would not only impact the foam stability, but also affect the setting behavior of CAC-containing foam slurries, consequently influencing the pore size and the heat-insulating property of the Al₂O₃ foamed ceramics. In this paper, modified polyethoxylated silicone (MPS), sodium alginate (SA) and carboxymethyl cellulose (CMC) were selected respectively as the foam stabilizer. The effects of the different foam stabilizers on the setting behavior of foam slurries, and the dependence of the pore size and heat-insulating property of CAC-bonded foamed ceramics on the setting behavior of foam slurries were investigated. It is found that SA promotes the hydration of CAC in the foam slurries, while MPS and CMC postpone the hydration of CAC in the foam slurries; and the foamed ceramics with SA have better structural integrity, higher porosity, smaller average pore size and lower thermal conductivity than those with MPS or CMC.     

Defect and microstructural evolution during drying of soapnut-based alumina foams

The present study demonstrates the use of soapnut, a naturally occurring surfactant for producing alumina ceramic foams. A range of slurry compositions with soapnut amounts ranging from 2 to 20 wt% in water, alumina loading of 35–55 vol% were studied. Though all slurry compositions foamed when subjected to mechanical agitation the formation of green ceramic foams free of macroscopic defects was found to be strongly dependent on conditions during drying of foamed slurries. Addition of guar gum to the slurries was shown to enhance foam stability and thus produce defect-free foams from compositions that otherwise either collapsed or resulted in other macroscopic defects during drying. Drying conditions also had a strong effect on microstructural parameters such as cell size and cell connectivity. Soapnut-based foams appear to have a greater connectivity between cells than foams produced by other comparable processes.     

Generation and characterization of carbon nano-fiber-poly(arylene ether sulfone) nanocomposite foams

In this study, carbon nano-fibers (CNFs) were used to increase the compressive properties of poly(arylene ether sulfone) (PAES) foams. The polymer composite pellets were produced by melt blending the PAES resin with CNFs in a single screw extruder. The pellets were saturated and foamed with water and CO₂ in a one-step batch process method. Dynamic mechanical thermal analysis (DMTA) was used to determine the reduced glass transition temperature (T_g) of the CNF-PAES as a result of plasticization with water and CO₂. Sharp transitions were observed as peaks in the tan δ leading to accurate quantitative values for the T_g. By accurately determining the reduced T_g, the foaming temperature could be chosen to control the foam morphology. Foams were produced which ranged in density from 290 to 1100 kg/m³. The foams had cell nucleation densities between 10⁹ and 10¹⁰ cells/cm³, two orders of magnitude higher than unreinforced PAES foam, suggesting that the CNFs acted as heterogeneous nucleating agents. The CNF-PAES foam exhibited improved compressive properties compared to unreinforced PAES foam produced from a similar method. Both the specific compressive modulus and strength increased by over 1.5 times that of unreinforced PAES foam. The specific compressive strength of 59 MPa for the CNF-PAES foam is similar to that of commonly used high performance structural foam, poly(methacrylimide foam).     

A new direct coagulation casting process for alumina slurries prepared using poly(acrylate) dispersant

Direct coagulation casting (DCC) of concentrated aqueous alumina slurries prepared using ammonium poly(acrylate) dispersant has been studied using MgO as coagulating agent. Addition of small amounts of MgO increased the viscosity of the concentrated alumina slurries with time and finally transformed it in to a stiff gel. Sufficient working time for degassing and casting could be achieved by cooling the slurries to a temperature of ∼5 °C after proper homogenization after the addition of MgO. The DCC slip with alumina loading in the range of 50–55 vol% showed relatively low viscosity (0.12–0.36 Pa s at shear rate of 93 s⁻¹) and yield stress (1.96–10.56 Pa) values. The wet coagulated bodies prepared from slurries of alumina loading in the range of 50–55 vol% had enough compressive strength (45–211 kPa) for handling during mould removal and further drying. The coagulated bodies prepared from slurries of alumina loading in the range of 50–55 vol% showed linear shrinkage in the range of 4.8–2.3 during drying and 17.1–16.2 during sintering respectively. Near-net-shape alumina components with density >98% TD could be prepared by the DCC process.     

Effect of pressure on early hydration of class H and white cement

The change in viscosity of cement slurry with temperature and pressure can be predicted by assuming that hydration can be treated as an activated process and that a given viscosity corresponds to a fixed degree of reaction. For Class H and White cements, chemical shrinkage experiments indicate that the activation energy is 33.8 kJ/mole and rheological measurements yield an activation volume of −30 cm³/mole. With these parameters, it is possible to predict the limit of pumpability of the slurry (which corresponds to a viscosity of about 2.5 Pa s) for arbitrary temperature and pressure cycles. This method of prediction requires that the physics of the process remain the same, but simply change in rate; therefore, the range of applicability is expected to be limited to temperatures below about 100 °C, since new phases occur at higher temperatures.     

Encapsulation of caesium-loaded Ionsiv in cement

The microporous material Ionsiv is used for ¹³⁷Cs removal from aqueous nuclear waste streams. In the UK, Cs-loaded Ionsiv is classed as an intermediate-level waste; no sentencing and disposal route is yet defined for this material and it is currently held in safe interim storage on several nuclear sites. In this study, the suitability of fly ash and blast furnace slag blended cements for encapsulation of Cs-Ionsiv in a monolithic wasteform was investigated. No evidence of reaction or dissolution of the Cs-Ionsiv in the cementitious environment was found by scanning electron microscopy and X-ray diffraction. However, a small fraction (≤ 1.6 wt.%) of the Cs inventory was released from the encapsulated Ionsiv during leaching experiments carried out on hydrated samples. Furthermore, it was evident that K and Na present in the cementitious pore water exchanged with Cs and H in the Ionsiv. Therefore, cement systems lower in K and Na, such as slag based cements, showed lower Cs release than the fly ash based cements.     

Utilising unprocessed low-lime coal fly ash in foamed concrete

This paper describes an extensive laboratory-based investigation into the use of unprocessed, run-of-station, low-lime fly ash in foamed concrete, as a replacement for sand. Foamed concrete with plastic densities ranging between 1000 and 1400 kg/m³ and cube strengths from 1 to 10 N/mm² were tested. It is shown that by using this type of fly ash in this way can significantly enhance many of the properties of foamed concrete, including rheology and compressive strength development, whilst providing almost complete immunity to sulfate attack. Given the high carbon content of this type of fly ash, however, it was found that there was a need to increase greatly the amount of foam required to achieve the specified design plastic density. However, given the relatively low cost of foam production, this is not likely to have significant implications for the use of material.     

Experimental measurement and numerical simulation of viscosity reduction effects in HMMPE containing a small amount of exfoliated organoclay-modified TLCP composite

A small amount (1 wt%) of organoclay-modified thermotropic liquid crystalline polymer (TLCP) acting as a viscosity reduction agent in high molecular mass polyethylene (HMMPE) was characterized and compared with purified TLCP (1 wt%) in HMMPE at 190 °C and 230 °C, respectively, where the TLCP displayed nematic and nematic-isotropic biphase structures. In the TLCP/PE blend at 190 °C and 230 °C, dramatic reductions in viscosity were observed with significant improvement in extrudate surface smoothness and an enlarged processing window. For the organoclay-modified TLCP in PE, the viscosity reduction ability of TLCP was further enhanced with viscosity dropped by up to >98.5% and >97.4% at 190 °C and 230 °C and processing window enlarged to >700 s⁻¹ and >900 s⁻¹ respectively in comparison to that of PE. Moreover, yielding stress, initial transition shear rate and transition region decreased to lower magnitudes than those of the TLCP/PE blend. A phenomenological model was applied to elucidate the mechanism of organoclay, TLCP and PE conformation before and after yielding in the confined capillary environment. A binary flow pattern model was applied to successfully predict the rheological behavior of the blends at 190 °C.     

Neural network (ANN) approach to biodiesel analysis: Analysis of biodiesel density, kinematic viscosity, methanol and water contents using near infrared (NIR) spectroscopy

The use of ethanol and biodiesel, which are alternative fuels or biofuels, has increased in the last few years. Modern official standards list 25 parameters that must be determined to certify biodiesel quality, and these analyses are expensive and time-consuming. Near infrared (NIR/NIRS) spectroscopy (4000-12,820 cm⁻¹) is a cheap and fast alternative to analyse biodiesel quality, when compared with infrared, Raman, or NMR methods, and quality control can be done in realtime (on-line).We compared the performance of linear and non-linear calibration techniques - namely, multiple linear regression (MLR), principal component regression (PCR), partial least squares regression (PLS), polynomial and Spline-PLS versions, and artificial neural networks (ANN) - for prediction of biodiesel properties from near infrared spectra. The model was created for four important biodiesel properties: density (at 15 °C), kinematic viscosity (at 40 °C), water content, and methanol content. We also investigated the influence of different pre-processing methods (Savitzky-Golay derivatives, orthogonal signal correction) on the model prediction capability. The lowest root mean squared errors of prediction (RMSEP) of ANN for density, viscosity, water percentage, and methanol content were 0.42 kg m⁻³, 0.068 mm² s⁻¹, 45 ppm, and 51 ppm, respectively. The artificial neural network (ANN) approach was superior to the linear (MLR, PCR, PLS) and “quasi”-non-linear (Poly-PLS, Spline-PLS) calibration methods.     

A new aluminium-hydrate species in hydrated Portland cements characterized by Al and Si MAS NMR spectroscopy

Recent ²⁷Al MAS NMR studies of hydrated Portland cements and calcium-silicate-hydrate (C-S-H) phases have shown a resonance from Al in octahedral coordination, which cannot be assigned to the well-known aluminate species in hydrated Portland cements. This resonance, which exhibits the isotropic chemical shift δ_iso = 5.0 ppm and the quadrupole product parameter P_Q = 1.2 MHz, has been characterized in detail by ²⁷Al MAS and ²⁷Al{¹H} CP/MAS NMR for different hydrated white Portland cements and C-S-H phases. These experiments demonstrate that the resonance originates from an amorphous or disordered aluminate hydrate which contains Al(OH)₆³⁻ or O_xAl(OH)_6-x^(3+x)− units. The formation of the new aluminate hydrate is related to the formation of C-S-H at ambient temperatures, however, it decomposes by thermal treatment at temperatures of 70-90 °C. From the experiments in this work it is proposed that the new aluminate hydrate is either an amorphous/disordered aluminate hydroxide or a calcium aluminate hydrate, produced as a separate phase or as a nanostructured surface precipitate on the C-S-H phase. Finally, the possibilities of Al³⁺ for Ca²⁺ substitution in the principal layers and interlayers of the C-S-H structure are discussed.     

Comparison of various radiation-cooled dew condensers using computational fluid dynamics

Radiation-cooled dew water condensers can serve as a complementary potable water source. In order to enhance passive dew collection water yield, a Computational Fluid Dynamics (CFD) software, PHOENICS, was used to simulate several innovative condenser structures. The sky radiation is calculated for each of the geometries. Several types of condensers under typical meteorological conditions were investigated using their average radiating surface temperature. The simulations were compared with dew yield measurements from a 1 m² 30°-inclined planar condenser used as a reference. A robust correlation between the condenser cooling ability and the corresponding dew yield was found. The following four shapes were studied: (1) a 7.3 m² funnel shape, whose best performance is for a cone half-angle of 60°. Compared to the reference condenser, the cooling efficiency improved by 40%, (2) 0.16 m² flat planar condenser (another dew standard), giving a 35% lower efficiency than the 30° 1 m² inclined reference condenser, (3) a 30 m² 30°-inclined planar condenser (representing one side of a dew condensing roof), whose yield is the same as the reference collector, and (4) a 255 m² multi-ridge condenser at the ground surface provided results similar to the reference collector at wind speeds below 1.5 m s^− 1 but about 40% higher yields at wind speeds above 1.5 m s^− 1.     

The effects of particle size distribution and surface area upon cement strength development

Particle size distribution, uniformity of the distribution and specific surface area (SSA) have a great influence on service properties of cement, particularly on strength. In this paper the effects of these physical parameters on strength development were studied using PC 42.5 R.In order to understand the significance of different particle size ranges in a distribution, samples having size distributions such as − 10 µm, − 20 µm, − 30 µm, − 45 µm, − 32 + 3 µm and − 20 + 5 µm were prepared from PC 42.5 R by using a laboratory scale 3rd generation separator. Additionally − 32 + 3 µm and − 20 + 5 µm fractions were added to the original PC 42.5 R in varying amounts to study SSA and uniformity effects. Same strength values were obtained for samples with a narrower size distribution but smaller SSA. Fineness is very important for strength development, particularly in the early stages of hydration.     

Foamability and viscosity behavior of extrusion foamed PLA–pulp fiber biocomposites

This study addresses the effect of fiber reinforcement, chain extension, and physical foaming agent type on foam morphology and viscosity behavior of pulp fiber reinforced poly(lactic acid) (PLA) biocomposites. PLA reinforced with 0, 10, and 20 wt % of bleached kraft pulp fibers with and without chain extender were foamed using two different physical foaming agents (carbon dioxide and isobutane) by extrusion foaming. Densities, foam morphologies, and viscosities were systematically analyzed and compared from the produced foams. As a conclusion, low-density foams are produced with both foaming agents and fiber levels, fiber addition limiting cell growth. Isobutane provides better dimensional stability with narrower cell size distribution, whereas carbon dioxide enables lower foaming temperature. Chain extension is essential to achieve foam with low density and good cell structure. Contrary to nonchain extended PLA, addition of fibers reduced the viscosity of chain extended PLA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48202.     

Rheology and properties of melt-processed poly(ether ether ketone)/multi-wall carbon nanotube composites

Poly(ether ether ketone) (PEEK)/multi-wall carbon nanotube (MWNT) composites containing up to 17 wt% filler were prepared using a twin screw extruder. Transmission electron microscopy (TEM) images reveal that the MWNTs were homogeneously dispersed in the PEEK matrix. Linear viscoelastic measurements show that both complex viscosity and moduli increase with increasing MWNT concentration. The storage modulus, G^′ exhibits a dramatic seven order increase in magnitude around 1 wt%, leading to a solid-like low-frequency behaviour at higher loadings; the effect can be attributed to network formation at a rheological percolation threshold. Rheotens measurements show that the melt strength also increases significantly on addition of nanotubes, however, the drawability decreases. An analytical Wagner model was used to calculate the apparent elongational viscosity over a wide range of elongational rates, and to reveal significant increases on addition of MWNTs, with a similar threshold behaviour. The electrical response is also dominated by percolation effects, increasing by nearly 10 orders of magnitude from 10⁻¹¹ to 10⁻¹ S/cm, on the addition of only 2 wt% MWNTs. In contrast, the thermal conductivity and tensile elastic modulus of the composites increased linearly with nanotube content, rising by 130% and 50%, at 17 wt% MWNTs, respectively.     

Aluminum-rich belite sulfoaluminate cements: Clinkering and early age hydration

Belite sulfoaluminate (BSA) cements have been proposed as environmentally friendly building materials, as their production may release up to 35% less CO₂ into the atmosphere when compared to ordinary Portland cements. Here, we discuss the laboratory production of three aluminum-rich BSA clinkers with nominal mineralogical compositions in the range C₂S (50-60%), C₄A₃$ (20-30%), CA (10%) and C₁₂A₇ (10%). Using thermogravimetry, differential thermal analysis, high temperature microscopy, and X-ray powder diffraction with Rietveld quantitative phase analysis, we found that burning for 15 min at 1350 ºC was the optimal procedure, in these experimental conditions, for obtaining the highest amount of C₄A₃$, i.e. a value as close as possible to the nominal composition. Under these experimental conditions, three different BSA clinkers, nominally with 20, 30 and 30 wt.% of C₄A₃$, had 19.6, 27.1 and 27.7 wt.%, C₄A₃$ respectively, as determined by Rietveld analysis. We also studied the complex hydration process of BSA cements prepared by mixing BSA clinkers and gypsum. We present a methodology to establish the phase assemblage evolution of BSA cement pastes with time, including amorphous phases and free water. The methodology is based on Rietveld quantitative phase analysis of synchrotron and laboratory X-ray powder diffraction data coupled with chemical constraints. A parallel calorimetric study is also reported. It is shown that the β-C₂S phase is more reactive in aluminum-rich BSA cements than in standard belite cements. On the other hand, C₄A₃$ reacts faster than the belite phases. The gypsum ratio in the cement is also shown to be an important factor in the phase evolution.     

Preparation of poly(ethylene terephthalate) nonwoven fabric from endless microfibers obtained by CO2 laser-thinning method

Poly(ethylene terephthalate) (PET) nonwoven fabric was prepared from microfibers obtained by using a carbon dioxide laser-thinning method. The PET nonwoven fabric obtained was made of the endless mircofibers with a uniform diameter without droplets. The fiber diameter can be varied by controlling airflow rate into the air jet and supplying speed of an original fiber into a laser-irradiating point. The fiber diameter decreased, and its birefringence increased as the airflow rate increased and the supplying speed decreased. When the microfiber prepared by irradiating the laser operated at a power density of 4.8 W cm⁻² to the original fiber supplied at S_s = 0.15 m min⁻¹ was dragged at an airflow rate of 30 L min⁻¹, the thinnest microfiber with a diameter of 3.6 μm was obtained.     

Gas foaming of segmented poly(ester amide) films

Biodegradable segmented poly(ester amide)s, based on dimethyl adipate, 1,4-butanediol and N,N′-1,2-ethanediyl-bis[6-hydroxy-hexanamide], with two distinct melting transitions were gas foamed using carbon dioxide (CO₂). Polymer films were saturated with CO₂ at 50 bar for 6 h after which the pressure was released. The samples were immersed in octane at the desired temperature after which foaming started immediately. Just above the lower melt transition the polymers retain adequate mechanical properties and dimensional stability, while the chain mobility increased sufficiently to nucleate and expand gas cells during the foaming process. In this way semi-crystalline poly(ester amide)s can be gas foamed below the flow temperature.Two poly(ester amide)s with 25 mol% (PEA2,5-25) and 50 mol% (PEA2,5-50) of bisamide segment content were foamed at 70 and 105 °C, respectively. The storage modulus (G′) of both pure polymers at the onset foaming temperature is 50-60 MPa. Closed-cell foams were obtained with a maximum porosity of ∼90%. The average pore size of PEA2,5-25 ranges from 77 to 99 μm. In contrast, the average pore size of PEA2,5-50 is in between 2 and 4 μm and can be increased to 100 μm by lowering the CO₂ saturation pressure to 20 bar. The porosity of PEA2,5-50 foams using this saturation pressure decreased to 70%.     

Effects of pore fractal structures of ultrafine coal water slurries on rheological behaviors and combustion dynamics

The ultrafine coal water slurry (CWS) with the particle size of 1-10 μm, ash content of 1-2%, solid concentration of 50% is a promising substitute fuel for diesel oil. The effects of pore fractal structures of three ultrafine CWSs on their rheological behaviors and combustion dynamics were studied in this paper. When the pore fractal dimensions of Yanzhou, Huainan and Shenhua ultrafine CWSs increase, their apparent viscosities all increase and the increase extents gradually enlarge with decreasing shear rates, while their ignition temperatures and apparent activation energies all decrease. For example, when the pore fractal dimension of Yanzhou coal increases from 2.31 to 2.43, the CWS apparent viscosity at a low shear rate of 12 s⁻¹ increases from 75 mPa s to 2400 mPa s, and that at a high shear rate of 100 s⁻¹ increases from 80 mPa s to 820 mPa s. Meanwhile, the ignition temperature of Yanzhou CWS decreases from 445 °C to 417 °C at a heating rate of 12.5 °C/min, and the apparent activation energy decreases from 104 kJ/mol to 32 kJ/mol.