Use of ceramic industry milling and glazing waste as an active addition in cement

The beneficial effects of pozzolans on cement manufacture have encouraged their use in that industry. Traditional natural pozzolan have become less available of late, however, due to a decline in quarrying intensity aimed at minimizing the impact on the landscape. At the same time, environmental policies pursue the reduction or elimination of spoil heaps by valorizing industrial waste and by‐products as raw materials, in keeping with the principles of the circular economy. The quest for new types of waste and by‐products with pozzolanic properties has consequently become a priority line of research. This study explored the valorization of one such by‐product, the ceramic sludge resulting from fired clay industry milling and glazing, as a component in new, more eco‐sustainable cements. The sludge was characterized physically, chemically, morphologically, and mineralogically to determine its suitability as a pozzolanic addition in cement. The findings showed that ceramic sludge consists in clustered particles ranging in size from 100 μm to 1 μm. SiO₂, Al₂O₃, and Fe₂O₃ together comprise over 70% of the total composition, while the reactive silica content is greater than the 25% required by the existing legislation. The predominant minerals are quartz, kaolinite, and muscovite, with some zircon. A study of pozzolanic reaction kinetics in the ceramic sludge/lime system revealed that over time this waste can fix lime, generating products such as calcium aluminate hydrates and C–S–H gels. The cements made with ceramic sludge proved to be standard‐compliant in terms of water demand, setting, drying shrinkage and mechanical strength.     

水泥基材料的水化动力学模型

介绍了水泥基材料的水化动力学模型.根据实验测定的水化放热数据,采用模型给出的积分和微分方程,对水泥基材料的水化反应中的3个基本过程即结晶成核与晶体生长(NG)、相边界反应(I)和扩散(D)进行了表征,得到反应速率常数K、反应级数n和表观活化能Ea等动力学参数以及各反应阶段的反应速率与反应度的关系.计算得到的各阶段的反应速率曲线能较好地分段模拟由量热实验得到的胶凝材料实际水化速率dα/dt曲线.观察3个阶段的相互关系,可对水泥基材料复杂的水化机理进行解释.水泥基材料的水化反应存在两种不同的历程:NG-I-D或NG-D.在水化初期NG是控制因素,随着水化程度提高,逐渐转由I或D控制反应.     

偏高岭土对硅酸盐水泥浆体干燥收缩行为的影响及机理

为探究偏高岭土（metakaolin,MK）影响水泥基材料干燥收缩（干缩）机理,研究了不同MK掺量（0、5％、10％、15％）、不同成熟度（水中分别预养护3d和28d）硅酸盐水泥浆体在20℃、55％相对湿度下的干缩和质量损失行为,并采用综合热分析和压汞法研究了不同成熟度水泥浆体的组成和微观结构。结果表明：MK对浆体干燥...     

辅助性胶凝材料反应程度与水泥力学性能关系研究

本文主要研究了矿渣和粉煤灰的比表面积以及掺量对水泥抗压强度的影响,并对矿渣和粉煤灰作为辅助性胶凝材料在水泥浆体中的反应程度与水泥力学性能之间的关系及反应机理进行了探讨,结果表明,随着粉煤灰、矿渣比表面积的增加,水泥的抗压强度增加,但比表面积有一个适合的范围;随着辅助性胶凝材料掺量的增加,水泥强度降低;单掺矿渣或粉煤灰,其反应程度与水泥抗压强度之间呈现良好的对数关系;复合掺加两种或两种以上的辅助性胶凝材料时,采用占主导地位的辅助性胶凝材料的反应程度与水泥抗压强度之间的关系来定性描述两者之间的内在联系,得出两者之间也呈现对数关系.     

Lightweight aggregate based on waste glass and its alkali-silica reactivity

The possible use of waste glass for the production of lightweight aggregate has been studied. The aggregate, in the form of highly porous granules, was produced by mixing together finely ground waste glass and an expansive agent and firing this mixture at a selected temperature. The expansive agent was chosen on the basis of the results of DTA/TGA experiments, which were carried out on some selected agents and confirmed by using a hot-stage microscope, where the temperature interval of the expansion was also determined. Pilot production of about 0.5 m³ of the aggregate was performed in a rotary kiln, and the water absorption and bulk density of the aggregate so obtained were determined. Special emphasis was placed on the determination of the alkali-silica reactivity of the aggregate, and the results of initial tests for alkali-aggregate reaction were encouraging, given the high potential reactivity of the material. However, before such aggregate can be considered safe for general use in concrete, longer-term concrete prism tests need to be carried out, which would cover the range of mixes in which the aggregate is likely to be used.     

Effect of network connectivity on behavior of synthetic Broborg hillfort glasses

There is wide industrial interest in developing robust models of long-term (>100 years) glass durability. Archeological glass analogs, glasses of similar composition, and alteration conditions to those being tested for durability can be used to evaluate and inform such models. Two such analog glasses from a 1500-year-old vitrified hillfort near Uppsala, Sweden have previously been identified as potential analogs for low concentration Fe-bearing aluminosilicate nuclear waste glasses. However, open questions remain regarding the melting environment from which these historic glasses were formed and the effect of these conditions on their chemical durability. A key factor to answering the previous melting and durability questions is the redox state of Fe in the starting and final materials. Past work has shown that the melting conditions of a glass-forming melt may influence the redox ratio value (Fe⁺³/∑Fe), a measure of a glass's redox state, and both melting conditions and the redox ratio may influence the glass alteration behavior. Synthetic analogs of the hillfort glasses have been produced using either fully oxidized or reduced Fe precursors to address this question. In this study, the melting behavior, glass transition temperature, oxidation state, network structure, and chemical durability of these synthesized glass analogs is presented. Resulting data suggests that the degree of network connectivity as impacted by the oxidation state of iron impacted the behavior of the glass-forming melt but in this case does not affect the chemical durability of the final glass. Glasses with a lower degree of melt connectivity were found to have a lower viscosity, resulting in a lower glass transition temperature and softening temperature, as well as in a lower temperature of foam onset and temperature of foam maximum. This lower degree of network connectivity most likely played a more significant role in accelerating the conversion of batch chemicals into glass than the presence of water vapor in the furnace's atmosphere. Future work will focus on using the results from this work with outcomes from other aspects of this project to evaluate long-term glass alteration models.     

废玻璃粉作为辅助胶凝材料对砂浆性能影响及作用机理

作为辅助胶凝材料掺入混凝土是废弃玻璃回收利用的途径之一。研究废玻璃粉掺料对砂浆性能影响及作用机理,结果可为该类应用提供指导。本文研究0~0.075 mm、0.075~0.15 mm和0.15~0.3 mm这三组不同粒径废玻璃粉作为辅助胶凝材料对砂浆力学性能及碱硅酸反应(ASR)膨胀作用的影响。研究发现:掺入玻璃粉粒径为0~0.075 mm可将砂浆28 d抗压强度增加5%~15%,ASR膨胀率减小20.2%;掺入玻璃粉粒径为0.15~0.3 mm则使砂浆28 d抗压强度降低5%~8%,ASR膨胀率增加39.7%。采用热重分析、等离子电感耦合、扫描电镜及能谱分析试验对反应产物、孔溶液、微观结构及其元素分布进行检测。分析认为粒径粗的玻璃粉碱骨料活性强,易发生ASR,导致膨胀率增加;粒径细的火山灰活性强,发生火山灰反应生成了膨胀率低的低钙硅比水化硅酸钙凝胶,该产物不仅会吸收Na⁺、K⁺,从而减少用于发生ASR的反应物含量,而且更密实,有利于降低孔隙率,减少水的渗透,提高抗压强度并抵抗膨胀压。     

煤矸石制备水泥辅助胶凝材料的应用研究

煤矸石制备水泥辅助胶凝材料的应用研究对水泥行业的节能减排与大宗固废的高值利用均具有重要意义。本文以河北某地不同矿区的6种煤矸石为原料,采用XRD,热重等方法分析判断其化学成分和矿物组成,通过静态煅烧实验研究了其煅烧活化条件,并通过胶砂实验测定其胶凝活性。结果表明,煅烧温度和时间会影响产品的胶凝活性,不同矿物组成的样品需要的煅烧条件不同,所测样品其3 d早期强度相较于基准水泥有所下降,但28 d活性指数增长明显,除#4矿区外均达到了制备辅助胶凝材料的要求。     

The influence of iodide on glass transition temperature of high-pressure nuclear waste glasses

The glass transition temperature (T_g) is a key parameter to investigate for application in nuclear waste immobilization in borosilicate glasses. T_g for several glasses containing iodine (I) has been measured in order to determine the I effect on T_g. Two series of glass composition (ISG and NH) containing up to 2.5 mol% I and synthesized under high pressure (0.5 to 1.5 GPa) have been investigated using differential scanning calorimetry (DSC). The I local environment in glasses has been determined using X-ray photoelectron spectroscopy and revealed that I is dissolved under its iodide form (I⁻). Results show that T_g is decreased with the I addition in the glass in agreement with previous results. We also observed that this T_g decrease is a strong function of glass composition. For NH, 2.5 mol% I induces a decrease of 24°C in T_g, whereas for ISG, 1.2 mol% decreases the T_g by 64°C. We interpret this difference as the result of the I dissolution mechanism and its effect on the polymerization of the boron network. The I dissolution in ISG is accompanied by a depolymerization of the boron network, whereas it is the opposite in NH. Although ISG corresponds to a standardized glass, for the particular case of I immobilization it appears less adequate than NH considering that the decrease in T_g for NH is small in comparison to ISG.     

A tetrad effect in the glass transition of lanthanide-doped sodium disilicate glasses

Scanning calorimetric determination of the glass transition temperatures (T_g) of sodium disilicate doped individually with 25 wt.% of the oxides of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu reveals the presence of the so-called “lanthanide tetrad effect” in their glass transition temperatures. This is to the best of our knowledge the first observation of a tetrad effect in the macroscopic properties of a high-temperature silicate phase.     

Effect of TiO2 and 11 minor elements on the reactivity of ground-granulated blast-furnace slag in blended cements

Ground-granulated blast-furnace slags (GGBS) are glasses (>99%) of the CaO-Al₂O₃-SiO₂ compositional system and are widely used as supplementary cementitious materials. Differences in reactivity of GGBS were screened by modifying the content of 12 minor elements (namely Ba, Ce, Cs, Cr, K, Mn, P, Sn, Sr, Ti, V, and Zr). Scanning electron microscopy observations showed that most elements entered the silicate glass matrix, only Sn was reduced to its metallic form and P accumulated in minor minerals. Mortar strength tests showed that 2 day compressive strength was reduced by >50% for a TiO₂ content of 2.5 wt% in the slag. At 28 days the loss in compressive strength was still >40%. Calorimetric tests on other element additions showed that the content of network modifiers (Ba, Cs, K and Sr) and GGBS reactivity are positively correlated, whereas Ce, Cr, V, and Zr significantly decreased reactivity. Finally, it is shown that these effects can be estimated by the concentration and the weighted field strength of the added element.     

Effect of glass composition on the hardness of surface layers on aluminosilicate glasses formed through reaction with strong acid

The effect of glass composition on physico‐chemical properties of surface layers formed through reaction between strong acid and several silicate and aluminosilicate glasses was studied through transmission‐IR, ATR‐IR, XPS, SIMS, and nano‐indentation analyses. It was shown that aluminum is depleted from the surface while molecular water is diffused into the surface layer of glasses with high levels of aluminum. Nano‐indentation experiments indicated that the hardness of the surface layers were decreased compared to that of the bulk region and the degree of the softening was more significant in the high aluminum glass.     

偏高岭土对水泥基胶凝材料耐久性能的影响

以粉煤灰、矿粉和硅灰为混合材,与硅酸盐水泥熟料和石膏复合制备一种水泥基胶凝材料,通过内掺法研究偏高岭土对水泥基胶凝材料力学性能和耐久性能的影响,并利用激光粒度分布曲线、XRD和SEM验结果表明,随偏高岭土掺量的增加,水泥砂浆3d强度逐渐下降,28d强度逐渐增加,然后趋于稳定。当掺量超过9%时,强度的改善效果不显著;同时,偏高岭土的掺入,提高了砂浆的抗渗性能、降低了混凝土的氯离子扩散系数,并在偏高岭土掺量为0%-9%范围内作用效果明显。     

Suppression of phosphor‐glass reactions in YAG:Ce phosphor‐embedded glasses

For high‐power white LED applications, YAG:Ce‐based yellow phosphors were embedded in a low‐T_g Bi₂O₃–B₂O₅–ZnO–Sb₂O₅ glass (BiG) by sintering route. A high‐T_g silicate glass (SiG) was also used for comparison. Dense (porosity<2%) phosphor‐glass composites were obtained after sintered at 800°C (for SiG) and 325°C (for BiG). XRD quantitative analysis indicates that the loss of phosphor content is in the range of 2.5%‐22%, caused by partial dissolution of phosphor particles into the glass matrix during sintering. The element distribution across the interface and within the reaction zone between phosphor and glass was analyzed by TEM/SEM‐EDS. The intrinsic emission characteristic of YAG:Ce is nearly not altered, possibly resulted from the slight modification of the YAG phase during sintering. Thus the final emission intensity of the sintered body is mainly determined by the residual amount of the YAG:Ce phase. Replace the high‐T_g SiG glass by the low‐T_g BiG glass, prenitridize the YAG:Ce phosphor, and change the sintering atmosphere from air to N₂ suppress the loss of phosphor during sintering. Therefore, the resulting loss of emission intensity of the phosphor‐embedded glass material can be reduced to only about 1.8%.     

The effects of Er:YAG laser treatment on the binding of glass ionomer cement to the prepared enamel

Conditioning of the enamel surface is a common strategy to improve the binding of restorative materials. Er:YAG is used broadly in clinics. However, whether it is beneficial to the binding of restorative materials is controversial. In the current report, we examined the effects of Er:YAG laser in improving the binding of the glass ionomer cement (GIC) to enamel surfaces. Briefly, 77 human premolar and molar teeth free of visible caries were used from the study and treated with different methods, including regular abrasion with diamond saw (Bur), 10 polyacrylic acid, 37% phosphoric acid, and/or Er:YAG laser. The shear bond strength (SBS) between GIC and enamel surfaces were measured; the patterns of the junction between GIC and enamel were observed by scanning electron microscopy (SEM); failure patterns were analyzed with stereomicroscope to determine the adhesive and cohesive patterns of the fracture. The results showed that the treatment of Er:YAG laser resulted in a higher SBS values than that of bur. The use of 10% polyacrylic acid could improve the GIC bonding to the bur-prepared enamel, but not for laser-prepared enamel surface. However, the treatment with 37% phosphoric acid increased the SBS dramatically both in bur-prepared and laser-prepared groups. The failure mold analysis and SEM observation demonstrated a cohesive failure within the cement. In conclusion, the treatment of Er:YAG laser was beneficial for the adhesion of GIC to enamel.     

Effect of self-etching dual-curing universal adhesive system application on bond strength of dentin resinous liners dentin

Purpose: The aim of this study was to evaluate the influence of previous application of an adhesive system on bond strength of resinous liner materials to dentin. Methods: Ninety bovine incisors crowns had a 6 × 6 mm area of dentin exposed, with minimum of 2 mm thickness. They were embedded in acrylic resin, and the dentin was polished with P600 SiC sandpaper for 30 s to standardize the smear layer. The specimens were divided into 6 groups (n = 15) according to the application or not of a self-etching system (Futurabond U – Voco) and the type of resinous liner used: A+Ionoseal (adhesive and Ionoseal – Voco); Ionoseal (Ionoseal only); A+Vitrebond (adhesive and Vitrebond – 3M/ESPE); Vitrebond (Vitrebond only); A+Ionosit (adhesive and Ionosit – DMG) and Ionosit (Ionosit only). Adhesives were used following manufacturer’s instructions, and the liner materials were applied inside a 2-mm-depth matrix and light-cured for 20 s. The bond strength was measured by microtensile test, using a universal testing machine with a cross-speed of 1 mm/min. Data were analyzed using one-way ANOVA and Tukey’s test (p < 0.05). Results: The adhesive system application increased bond strength of all liners tested. Ionoseal presented the highest bond strength when the adhesive system was used and exhibited similar performance to Vitrebond without adhesive. Ionosit without adhesive showed the smallest bond strength compared with the other liners tested. Conclusion: The application of an adhesive system prior to the use of the resinous liners improved the bond strength to dentin and should be preconized.     

高掺量矿物掺合料对水泥基材料固化氯离子能力的影响

本文研究了高掺量矿物掺合料对水泥基材料固化氯离子能力的影响,并借助XRD、DTG等进行了分析,研究结果表明:在水泥掺量为20％情况下,随着矿粉和NaCl的掺量的增加,提高了水泥基材料的强度.高掺量的矿粉促进了水泥基材料中的F盐和镁铝水滑石的生成提高了其对氯离子的固化能力,增加浆体的水灰比对氯离子的固化也起到了促进作用.     

The kinetic analysis of irreversible consecutive solid state reactions: The effect of zinc on the formation of cordierite

Many reactions in the solid state occur in multiple reaction steps. Here, I present a method of determining the kinetics of a two‐step consecutive reaction from isothermal, time resolved, powder diffraction data. This method is illustrated with a study of the kinetics of the formation of cordierite from a glass precursor with and without doping with zinc.     

The fracture toughness of inorganic glasses

Measuring the fracture toughness (K_Ic) of glasses still remains a difficult task, raising experimental and theoretical problems as well. The available methods to estimate K_Ic are reviewed, with emphasis on their respective advantages and drawbacks. In view of our current understanding, this analysis gives precedence to the SEPB method. The ultimate glass strength, the critical flaw size, and the indentation load for the onset of crack initiation are discussed, in the light of the fundamentals of fracture mechanics and classical background regarding the mechanics of brittle materials. Analytical expressions were further proposed to predict the fracture energy and fracture toughness of glasses from different chemical systems from their nominal compositions. The theoretical values were compared with the experimental ones, as obtained by self‐consistent methods when available. The agreement observed in most cases suggests that measured K_Ic values correspond to the crack propagation regime (as opposed to the crack initiation threshold), and supports previous investigations in glasses and ceramics, which showed that a crack tip is nearly atomically sharp in these materials (but for metallic glasses). Some ideas to design tougher glasses are finally presented.