The effect of high curing temperature on the reaction kinetics in MK/lime and MK-blended cement matrices at 60 °C

It is well known that the pozzolanic reaction between metakaolin (MK) and calcium hydroxide produces CSH, C₂ASH₈ (stratlingite), C₄AH₁₃ and C₃ASH₆ (hydrogarnet). However, the presence or absence of these hydrated phases depends on different parameters, such as curing temperature, matrix used, etc. This paper shows the results of a study in order to know the effect of high curing temperature (60 °C) on the kinetics of the pozzolanic reaction in different matrices. MK/lime (calcium hydroxide) and MK-blended cement matrices were studied in samples stored and cured at 60 °C and up to 123 days of hydration. The nature, sequence and crystallinity of the hydrated phases were analysed using differential thermal analysis (DTA) and X-ray diffraction (XRD) techniques.Results showed that the sequence and formation of the hydrated phases was different in both matrices cured at 60 °C. In an MK/lime matrix, C₂ASH₈, C₄AH₁₃ and C₃ASH₆ were the main hydrated phases; while in an MK-blended cement, stratlingite was the sole hydrated phase issued from pozzolanic reaction. The DTA and XRD data also reveal an important fact: there is no evidence of the presence of hydrogarnet in blended cements.     

Pozzolanic behaviour of compound-activated red mud-coal gangue mixture

The pozzolanic behaviour of compound-activated red mud-coal gangue has been investigated through TG, DTA, XRD, FTIR and ²⁷Al MAS NMR. From viewpoint of reaction kinetics, it is found that the pozzolanic reaction mechanism of the compound-activated red mud-coal gangue — lime system is clearly consistent with diffusion control up to 14 days, and the reaction rate constant calculated from Jander equation decreases with the increase of CaO addition in the system. The hydration products formed in the red mud-coal gangue — lime systems at ambient temperature are essentially aluminous C–S–H and Ca₃Al₂O₆.xH₂O. From TG analysis results, it is thought that the high amount of Ca(OH)₂ in the pastes of studied system is not conducive to the continual increase of non-evaporable water content of the hydration products. Of particular interest, ²⁷Al MAS NMR proved to be an effective technique to obtain valuable information of Al^[4] in C–S–H and Al^[6] in Ca₃Al₂O₆.xH₂O.     

Study of hydrated phases present in a MK-lime system cured at 60 °C and 60 months of reaction

This research presents the experimental results of a study carried out to determine the effect of curing temperature on the reaction kinetics in a metakaolin/lime mixture cured at 60 °C and after 60 months of hydration. The stabilities of hydrated phases formed during the pozzolanic reaction in these working conditions were evaluated. The results obtained in current paper showed that metastable hexagonal phases (C₂ASH₈ and probably C₄AH₁₃) coexist with stable cubic phase (hydrogarnet) in the absence of lime. Also, there is evidence of the possible presence of a calcium aluminum silicate hydroxide hydrate (vertumnite).     

A study on the hydration properties of high performance slag concrete analyzed by SRA

The synchrotron radiation accelerator (SRA) was used to analyze the hydration properties of high performance slag concrete in this study. The results show that, as the water to binder ratio increases, the speed of hydration of alite and C₃A increase, as do the formation rates of CH and ettringite (AFt). Also, if the content of slag produces pozzolanic reaction, then the formation rate of CH will decrease, especially when the age increases. In short, the structures of CH, AFt and AFm can be analyzed both qualitatively and quantitatively by SRA.     

The effect of dehydroxylation/amorphization degree on pozzolanic activity of kaolinite

The effect of heat treatment parameters on the dehydroxylation/amorphization process of the kaolinite-based materials such as natural and artificial kaolin clays with different amounts of amorphous phase (metakaolin) was investigated. The procedure for quantitative estimation of amorphous phase in the heat-treated kaolinite materials was developed. The process of dehydroxylation/amorphization of kaolinite was characterized by DTA/TGA with mass-spectrometry and X-ray powder diffraction. The influence of the heat treatment temperature and content of the amorphous phase on pozzolanic activity was studied. Finally, the relationships between the chemical activity, activity strength index and the amorphous phase content were found and discussed. The results obtained are important for an optimization of the process of the metakaolin large scale production and it's use as an active pozzolanic admixture.     

Hydration behaviour, structure and morphology of hydration phases in advanced cement-based systems containing micro and nanoscale pozzolanic additives

This paper deals with the early hydration and structure development aspects of advanced cement-based systems that contain micro and nanoscale pozzolanic additives. We have used highly reactive colloidal silica produced by pyrogenic route (pyrogene oxides) as representative of nanoscale pozzolanic additives. Colloidal silica shortens the induction period to an extent that can be qualitatively correlated to the size of its primary silica particles and the specific surface area. Colloidal silica accelerates the early hydration reactions by providing large amounts of reactive siliceous surface, which serves as a site for the early C-S-H precipitation. Additionally the use of pozzolanic additives as cement replacement smoothes and reduces the heat of hydration evolved. The high performance specimens that contain microscale additives and especially those that contain both micro and nanoscale additives are characterised by very tight structure and are made up of finer structures in closer contact than the normal performance specimen without pozzolanic additive.     

The hydration characteristics of MSWI fly ash slag present in C3S

This paper reports on an investigation of the hydration characteristics of C₃S and the mixing of C₃S with municipal solid waste incinerator (MSWI) fly ash slag. The results can be summarized as follows: TGA observations show lower amounts of CSH and Ca(OH)₂ in samples that incorporated MSWI slag into C₃S, possibly due to the partial replacement of the C₃S by slag with less activity. In general, the incorporation of slag into C₃S decreases the initial hydration reactions, but it increases the pozzolanic reactions at a later stage by consuming Ca(OH)₂. As the hydration precedes, the C₃S peaks decrease, up to 90 days, due to the activation of the slag by liberated Ca(OH)₂. As well, the amount of hydration products (Ca(OH)₂) from the pure C₃S pastes are more than for the C₃S-slag pastes. Moreover, the degree of hydration of the C₃S pastes increases with the curing time, the C₃S-slag paste also shows that lower hydration degree values at all ages.     

CaO基的制备及温度对吸收率的影响

以石灰石和生料为原料,制备CaO吸收剂,用综合热重分析仪,研究温度对吸收剂吸收率的影响。结果显示,初始反应阶段,钙基吸收率在不同的温度下随反应时间都快速增加,温度升高时,钙基吸收率增加更快;产物层扩散控制阶段,温度750℃时,吸收率随反应时间延长基本没有变化,曲线趋于平缓,吸收反应速率很小,且不同温度下的样品吸收率变化趋势相同,都无太大增加。     

乙二醇反应精馏选择性与常规水合比较

重点介绍了乙二醇反应精馏的理论基础，并与常规水合工艺生成乙二醇的选择性进行了比较，从理论上说明了反应精馏选择性高于常规水合的原因。     

Co—Cr—Mn—Fe系黑颜料的高温呈色稳定性研究

利用晶体场理论，对Ｃｏ２Ｏ３－Ｃｒ２Ｏ３－ＭｎＯ２－Ｆｅ２Ｏ３系高温黑颜料在基础釉中的呈色稳定性进行了定性分析，确定了该系颜料呈色稳定性的主要影响因素及最佳工艺条件，这对该系颜料的生产和正确使用有很重要的理论指导作用     

Influence of metastable hydrated phases on the pore size distribution and degree of hydration of MK-blended cements cured at 60 °C

When MK reacts with calcium hydroxide, cementitious products are formed. It has been reported that CSH, C₂ASH₈ and C₄AH₁₃ are the most important hydrated phases formed. These phases are stable at 20 °C. However, some of them (C₂ASH₈ and C₄AH₁₃) are metastable phases, converting to hydrogarnet (C₃ASH₆) for long curing times at elevated temperatures. The partial or total conversion reaction could produce a negative effect on the performance and durability of blended cements, due to a volume decrease associated with the process of transformation.Due to the influence that this conversion could have on the microstructure and durability of a cement paste containing MK, the current paper presents the results of a research programme carried out on blended cements containing 10%, 20% and 25% of MK, cured at 60 °C up to 124 days of hydration.The total, partial porosity and average pore diameter evolution vs. time is determined using mercury intrusion porosimetry (MIP). An estimated degree of hydration of MK-blended cements cured at 60 °C is proposed.The results show that there is no increase in porosity values and average pore diameters with time. Therefore, the hydrated phases produced in MK-blended cements under the test conditions used do not have a negative effect on the microporosity. A suitable correlation between porosity and degree of hydration has been found.     

不同煅烧温度下形成的含氟硫A矿对水泥水化性能的影响

为研究不同煅烧温度下，含氟硫熟料中不同性能、形貌特征的A矿与水泥水化形成钙矾石的关系以及A矿对水泥水化性能的影响，采用工业原料并尽量模拟立窑内煅烧状况，对经1350℃和1425℃温度下煅烧的熟料进行了A矿形貌、A矿水化率及A矿与钙矾石形成关系等系列试验。试验结果表明，在传统的煅烧温度下（1400～l425℃）烧成的熟料．其A矿的固溶程度及A矿含量均比低温（1350℃）烧成的高；掺氟硫复合矿化剂烧制的熟料的A矿具有较高的水化速度，熟料强度较高．其制成的水泥在水化时，液相成分受高固溶程度A矿的水化所控制，所形成的钙矾石较低温煅烧的稳定．且A矿水化产物的形成与钙矾石（AFt）的形成较协调，水泥石机械强度更高。     

The effect that different pozzolanic activity methods has on the kinetic constants of the pozzolanic reaction in sugar cane straw-clay ash/lime systems: Application of a kinetic-diffusive model

The reaction kinetics of a mixture of sugar cane straw with 20% and 30% of clay burned at 800 and 1000 °C and lime (calcium hydroxide) is studied. A direct method (accelerated chemical method) based on the measurement of the amount of lime reacted as the reaction proceeds is applied. A kinetic-diffusive model published in a previous paper by some authors of this research is used. The fitting of the model by computerized methods allows determining the kinetic coefficients that characterize the process: in particular, the reaction rate constant. The index of pozzolanic activity evaluated according to the obtained values of the reaction rate constant permits to characterize the pozzolanic activity of these materials in a rigorous way. The results are compared with the results obtained applying an indirect method (conductometric method). The kinetic results obtained in the current paper allow affirming that the kinetic-diffuse model used in order to evaluate the pozzolanic reaction is valid, independently of the method used for the evaluation of the pozzolanic activity.     

钛系催化剂对聚酯缩聚反应速度和热稳定性影响的研究

研究了K2TiF6、(C4H9O)4Ti、Sb2O33种催化剂的缩聚反应速度,并对3种催化剂合成的切片进行了热稳定性比较(Δ[η]、TG)。结果表明:钛系催化剂的催化活性明显高于常规Sb2O3,其中以(C4H9O)4Ti的催化活性最高;(C4H9O)4Ti的动力学曲线具有阶段性,其高催化活性体现在缩聚反应的中后期;对3种催化体系制得的PET切片进行热稳定性测试的结果表明:采用(C4H9O)4Ti作为催化剂配合稳定剂SI与Co2+可制得色相良好,热稳定性高的聚酯切片。     

大庆某低渗轻质油藏注空气低温氧化反应动力学研究

轻质油藏注空气提高采收率的机理之一是在油藏中发生低温氧化反应,低温氧化反应进行的程度将对油藏注空气开发的可行性产生决定性的影响。通过在RUSKA2370-601PVT筒中进行的大庆某低渗油田原油与空气恒温恒压氧化反应实验数据,获得轻质油藏注空气低温氧化反应动力学参数为:原油氧化反应为零级反应;21 MPa,87℃时氧化反应的速度常数KO2为1.2255×10-4mol/(mL.h),21 MPa,127℃时氧化反应的速度常数KO2为7.0101×10-4mol/(mL.h),原油样品的阿仑尼乌斯活化能Ea为52.1 kJ/mol。     

Effect of cure temperature on the formation of metakaolinite-based geopolymer

A series of metakaolinite-based geopolymer was prepared at several curing temperatures and its relationship with porosity, infrared spectrometry (FT-IR) and mechanical properties was investigated. The samples were cured at the following temperatures: 55, 65 and 80 °C for 1 h. After a post cure of 28 days, the samples were investigated by using the following techniques: compressive strength, mercury intrusion porosimetry (MIP), helium pycnometry, X-ray diffraction (XRD), scanning electron microscopy (SEM) and infrared spectrometry (FT-IR). All samples were amorphous by XRD. The sample thermally treated at 65 °C (C65) presented the highest values of compressive strength and relative integrated area of peak at 792 cm⁻¹. This peak was attributed to a higher concentration of tetra-coordinated aluminum, indicating a higher efficiency of the geopolymeric reaction. The C65 also presented the lowest volume of closed pores. The values of the skeletal and the true densities for C65 were very similar and consistent with the volume of the closed pores. On the other hand, this sample showed the highest bulk density obtained by MIP and the greatest difference between the open and closed porosity measured by MIP and helium pycnometry, respectively. All these results are coherent and clearly indicate that the amount of open pores is directly related to a better mechanical performance of the geopolymeric sample.     

Deposition rate and temperature of carbon films during laser-induced CVD on a moving substrate

The feasibility of using pyrolytic laser-induced chemical vapor deposition (LCVD) to deposit carbon coatings on moving fused quartz substrates is investigated. This LCVD system uses a CO₂ laser to locally heat a substrate in open air to create a hot spot. Pyrolysis of hydrocarbon species occurs and subsequently deposits a layer of carbon film onto the substrate surface. The results of this study indicate that growth kinetics and the geometry of uniform carbon stripes deposited by pyrolytic LCVD strongly related to the laser power, the traverse velocity of the substrate, the type of hydrocarbon species used in deposition, and the diameter of the substrate. The deposition rate of carbon film increases exponentially with the laser power, while an increase in traverse velocity of the substrate will also increase the deposition rate until a maximum deposition rate is reached; further increases in the traverse velocity will decrease the deposition rate. We suspect that this optimal deposition rate is caused by substrate motion, which affects the substrate surface temperature, and consequently the effective surface area available for film deposition. The substrate temperature is observed to behave linearly with the deposition parameters considered in this study.     

The kinetic analysis of the thermal decomposition of kaolinite by DTG technique

The thermal decomposition of kaolinite was studied by differential thermogravimetry (DTG) technique under non-isothermal conditions. Samples of industrially treated (washed) kaolin with high content of the medium ordered kaolinite were calcined using a heating rate from 1 to 40 K min^− 1. The apparent activation energy and frequency factor for the dehydroxylation of kaolinite was evaluated by Kissinger method as 195 ± 2 kJ × mol^− 1 and (8.58 ± 0.33) × 10¹⁴ s^− 1, respectively. Avrami exponent of the process was estimated using Kissinger empirical kinetic models and Carne equation.     

杂质对DTBP热稳定性影响的研究

为研究杂质对二叔丁基过氧化物(DTBP)热稳定性的影响,利用C600微量热仪对DTBP与杂质的混合物进行热分解动力学试验研究,测定了纯DTBP在不同升温速率下及其与杂质的混合物在0.5K·min-1升温速率下的起始放热温度和分解热,并计算得到DTBP热分解反应的动力学参数。依据Arrhenius定律和化学反应理论确定了其与水、混合酸、NaOH、NaCl、铁和橡胶等杂质混合后活化能以及指前因子,研究表明,水、混合酸、NaOH、NaCl的加入使DTBP的活化能有增加的趋势,而铁和橡胶则在一定程度上降低了活化能,结合自加速分解温度(SADT)值进一步证明,水、混合酸、NaOH、NaCl对DTBP的稳定性没有影响,铁和橡胶对DTBP热稳定性影响最大。     

Sintering temperature effect on microstructure,electrical properties and temperature stability of MnO-modified KNN-based ceramics

Lead-free 0.955K_0.5Na_0.5NbO₃-0.045Bi_0.5Na_0.5ZrO₃?+?0.6%MnO (KNN-0.045BNZ?+?Mn0.6) ceramics have been prepared by a conventional solid-state sintering method in air. All the samples sintered at different temperatures possess a coexisting phase boundary (CPB) between rhombohedral (R) phase and tetragonal (T) phase. The increase of sintering temperature (T_s) increases the phase fraction of T phase in CPB region. Mn²⁺, Mn³⁺ and Mn⁴⁺ ions coexist in all the KNN-0.045BNZ?+?Mn0.6 ceramics sintered at 1110?°C to 1190?°C. High sintering temperature can induce a transformation from ${\mathrm{M}\mathrm{n}}_{\mathrm{N}\mathrm{b}}^{\text{'}\text{'}}$ defects to ${\mathrm{M}\mathrm{n}}_{\mathrm{N}\mathrm{b}}^{\text{'}}$ defects. The samples with fine grain show stable octahedral structure. The KNN-0.045BNZ?+?Mn0.6 ceramics with fine grain possess excellent temperature stability of $d_{33}^{*}$ due to the wide phase transition region. The increase of sintering temperature induces the (R-T) phase transition temperature to move to room temperature.