Portland-limestone cements. Their properties and hydration compared to those of other composite cements

The new European Standard EN 197-1 emphasizes the development of composite cements. In Greece a variety of pozzolanic and/or hydraulic materials are used as cement main constituents. Until now, limestone could be used only as a filler (up to 3% w/w), but since 2001 (application of EN 197-1) it can also be used as a main cement constituent. In this work a comparison between limestone and some of the materials that are already used in Greece is presented. An ordinary Portland cement and three Portland-composite cements containing limestone, natural pozzolana or fly ash were produced. The grinding process was designed in order to produce cements of the same 28 day compressive strength. The mechanical and physical properties of the cements were measured and hydrated products, formed after 1–28 days, were identified by means of XRD. The composite cements present significant differences as far as the clinker fineness, the development of the strength, the water demand and the hydration rate is concerned. The production of Portland-limestone cements seems to be very challenging, due to the satisfactory properties of the limestone cements as well as the low cost and the high availability of limestone in Greece.     

Nanoamorphous carbon as a blackbody source in plasmonic thermal emitters

Ag/dielectric/Ag-type plasmonic thermal emitters (PTEs) following a hexagonal lattice were fabricated, and their plasmonic emission spectrums were characterized with Fourier transform infrared spectroscopy. Nanoamorphous carbon (NAC) is used as a dielectric layer. Doping NAC with various materials over a wide range of levels enables control of the resistivity of the composite films where MoSi(2) was selected as the dopant. Wavelength tuning in the range of 4-7 μm is demonstrated by changing the conductivity of the composite films as well as the lattice periodicity of the hexagonal lattice. We also tested the mechanical stability of the PTEs under mechanical strains.     

From a two-dimensional chemical pattern to a three-dimensional topology through selective inversion of a liquid-liquid bilayer

Soft organic surfaces with more and more complex topologies are required daily to engineer appropriate microstructures for many different applications such as DNA array technology, biological optics for advanced photonic systems and microfluidics. Complementarily to conventional lithographic processes, several pioneering methods have been developed recently, by controlling phase separation of polymer blends, spinodal decomposition of homopolymers or by using the action of additional external forces driving diverse instabilities. Here we present a method that not only provides original concepts towards the three-dimensional (3D) structuring of liquids, on the basis of the synergistic effects of molecular diffusion and confined nucleation, but also suggests original solutions for the transport, mixing and filtering of small volumes of liquid. Through the intrinsic destabilization of a liquid-liquid bilayer, the 2D pattern of a chemically structured surface with 'hydrophilic' and 'hydrophobic' domains is transferred to a solid/liquid interface as a 3D topography with either 'positive' or 'negative' replication. This easy-to-use process has potential applications in various technological realms requiring a specific topography at interfaces such as microfluidics or biosensors.     

Morphology and growing of nanometric multilayered films formed by alternated layers of poly(3,4-ethylenedioxythiophene) and poly(N-methylpyrrole)

Multilayered nanometric films formed by alternated layers of conducting poly(3,4-ethylenedioxythiophene) and poly(N-methylpyrrole) doped with perchlorate anions (ml-PEDOT/PNMPy) have been prepared using a layer-by-layer electrodeposition technique combined with a very small polymerization time. The mechanisms of formation and growth of the resulting multilayered systems have been investigated using Atomic Force Microscopy (AFM), and compared with those obtained for the corresponding homopolymers, which were prepared using identical experimental conditions. Furthermore, the local conductivity, electroactivity and electrostability have been also examined. Analyses of the morphology, topography and roughness of the surfaces indicate that the formation and growth of the multilayered films strongly depend on the number of layers as well as on the chemical nature of the conducting polymer. Interestingly, AFM reflects that the formation and growth of the ml-PEDOT/PNMPy films are significantly different from those of PEDOT and PNMPy homopolymers. The electrical and electrochemical properties of the systems under study are fully consistent with the proposed mechanisms. Results evidenced that multilayered systems formed by two conducting polymers are more advantageous from a technological point of view than the corresponding copolymers.     

近化学计量比LiNbO3晶体电畴结构观察和机理探讨

采用双坩埚提拉法(DCCZ)生长了各种不同成分的近化学计量比LiNbO₃晶体, 并用腐蚀法观察了其电畴结构. 结果表明, 化学成分对未经极化处理晶体的电畴结构起决定性作用, 当Li₂O 含量处于49.4mol%附近时, 晶体z面电畴呈现特殊的三次对称反畴; 当晶体中Li₂O含量为49.7mol%时, 晶体为完全单畴. 本文对其形成机理进行了探讨, 认为在由顺电相向铁电相转变 时, 局部铁电畴的极性方向与该处沿z轴方向的温度梯度正负密切相关, z轴生长晶体时, 由于相变发生所处位置离生长界面的距离受LiNbO₃晶体计量比影响, 所处温场固有温梯也 随之不同, 在此基础上解释了不同成分晶体的电畴结构形成原因. 最后讨论了控制铁电畴结构的工艺措施.     

The effect of metakaolin on the corrosion behavior of cement mortars

In this paper the effect of metakaolin addition on the corrosion resistance of cement mortar is studied. A poor Greek kaolin with a low kaolinite content was thermally treated and the produced metakaolin (MK) was ground to the appropriate fineness. In addition, a commercial metakaolin (MKC) of high purity was used. Several mixture proportions were used to produce mortar specimens, where metakaolin replaced either sand or cement. Mortar specimens were then exposed to the corrosive environment of either partial or total immersion in 3.5% w/w NaCl solution. For the evaluation of the performance of metakaolin, the following methods were used: compressive strength, corrosion potential, mass loss, electrochemical measurements of the corrosion rate by the Linear Polarization method, carbonation depth and porosity. It is concluded that metakaolin improves the compressive strength and the 10% w/w addition shows the optimum contribution to the strength development. In addition, the use of metakaolin, either as a sand replacement up to 20% w/w, or as a cement replacement up to 10% w/w, improves the corrosion behavior of mortar specimens, while when metakaolin is added in greater percentages there is no positive effect.     

Characterization of the fine fraction of the argon oxygen decarburization with lance (AOD-L) sludge generated by the stainless steelmaking industry

The argon oxygen decarburization with lance (AOD-L) sludge generated by the stainless steelmaking industry is a hazardous waste due to the presence of chromium. While its coarse fraction is usually recycled into the own industrial process, the fine fraction is normally disposed in landfills. Techniques such as briquetting or magnetic separation were found to be inadequate to treat it for reuse purposes. So, in this work, the fine fraction of the AOD-L sludge was characterized aiming to find alternative methods to treat it. This sludge consists of a fine powder (mean diameter of 1 microm) containing 34 +/- 2% (w/w) of iron, 10.2 +/- 0.9% (w/w) of chromium and 1.4 +/- 0.1% (w/w) of nickel. The main crystalline phases identified in this study were chromite (FeCr(2)O(4)), magnetite (Fe(3)O(4)), hematite (Fe(2)O(3)) and calcite (CaCO(3)). In the digestion tests, the addition of HClO(4) has favored the dissolution of chromite which is a very stable oxide in aqueous media. Nickel was found in very fine particles, probably in the metallic form or associated with iron and oxygen. The sludge was classified as hazardous waste, so its disposal in landfills should be avoided.     

Viscoelastic properties of poly(butylene terephthalate)/poly(ethylene naphthalate) blends

Melt blends of poly(butylene terephalate) (PBT) and poly(ethylene naphthalate) (PEN) with 30 and 60 wt% PEN were prepared using a single screw extruder and an injection moulding machine. Stress relaxation tests for the specimens of PBT/PEN blends and the homopolymers were carried out using an Instron testing machine in an Instron environmental chamber. The Taguchi method of experimental design analysed how different levels of temperature, PEN content and initial stress affected the relaxation behaviour of PBT/PEN blends and homopolymers. From the response tables and analyses of main and interaction effects, it was shown that the most significant factor was temperature, followed by PEN content and then the initial stress. Consequently, high temperature, low PEN content and high initial stress speeded up stress relaxation rate of specimens. Interaction effects between factors were insignificant. To fit the relaxation curves of the PBT/PEN blends and the homopolymers at different temperatures, PEN contents and the initial stresses, four different equations were attempted with Matlab™, which determined the coefficients of these functions using the experimental data of stress change with time. The simulated curves from the most suitable function among them were shown using the calculated coefficients to predict the relaxation behaviour of PBT/PEN blends (50% PEN) at temperatures of 30 and 60°C with an initial stress of 7 MPa.     

硫醇@三聚氰胺甲醛树脂/环氧树脂固化剂的制备及性能表征

采用三聚氰胺-甲醛树脂(PMF)为壁材,三羟甲基丙烷三(3-巯基丙酸酯)(TMPMP)作为芯材,原位乳液聚合法制备了硫醇@三聚氰胺甲醛树脂(TMPMP@PMF)微胶囊固化剂。研究了乳化剂种类及用量,囊壁质量比,反应温度,反应时间,pH值对合成TMPMP@PMF微胶囊粒径及稳定性等影响。结果表明:当反应乳液中芯材的质量分数达到2wt%,同时芯材与壁材的单体质量比达到2∶1时,能制备出粒径在大约100μm,粒径均匀的TMPMP@PMF微胶囊。TMPMP@PMF微胶囊的结构稳定,耐热性好,并且呈闭孔结构。采用TMPMP@PMF微胶囊为固化剂,与环氧树脂(EP)基体混合配制成压敏型TMPMP@PMF/EP固化剂,发现微胶囊结构在受到外力作用时能及时破裂,室温甚至低温下都能短时间使环氧树脂固化,并且能够很好地改善固化剂的抗冲击性能。     

营商环境、科技创新与经济高质量发展 ——基于对外开放调节效应的省级面板数据实证分析

基于2011-2017年省级面板数据,在理论上分析了营商环境对经济高质量发展的作用机理,并考察了对外开放对科技创新与经济高质量发展之间关系的影响。研究结果发现:良好的营商环境能显著促进经济高质量发展;机制分析表明,营商环境能通过提高科技创新水平来促进经济高质量发展;进一步分析表明,对外开放会显著促进经济高质量发展,但会削弱科技创新对经济高质量的正向促进效应,尤其对我国科技含量较高的专利。其政策含义是,我国应持续优化营商环境,继续鼓励科技创新,提高自主研发能力与对外开放质量。     

Compressive strength development of binary and ternary lime–pozzolan mortars

This study considers the compressive strength development of broad range of hydraulic lime mortars prepared with a range of commercially available alumino-silicate by-products and modern pozzolanic additions. Specifically this paper considers the effect of mineral addition selection, binary and ternary combinations, pozzolan content and the effect of curing conditions on the compressive strength development of hydraulic lime based mortars. The study was undertaken as the initial phase of a broader investigation considering the feasibility of producing modern, sustainable hydraulic lime–pozzolan concretes with comparable strengths to Portland cement based concretes. The aim of the initial phase was to identify a small number of additions, and combinations thereof, which would result in a structural strength lime–concrete when scaled up from mortars to concretes.In the absence of a definitive source of information on the mechanical properties of hydraulic-lime mortars prepared with binary and ternary combinations of alumino-silicate by-products, 22 combinations consisting of Natural Hydraulic Lime (NHL5) and a range of possible additions, identified from historical and current practice, were prepared. The results have shown that combining an eminently-hydraulic NHL5 with silica fume and ground granulated blastfurnace slag can produce mortars with a 28-day compressive cube strength of around 28 N/mm², at a water-to-binder (w/b) ratio of 0.5. This is eight times the strength of an equivalent mortar prepared with NHL5 alone and broadly speaking comparable with that of low-heat cementitious mortars. The contribution of the pozzolanic reaction to the strength of hydraulic lime mortars is discussed for a range of alumina-silicious materials and combinations thereof.     

Phase equilibrium,microstructure and properties of some magnesite-chromite refractories

The effect of phase equilibrium and microstructure of magnesite-chromite batches containing from 0 to 100% Egyptian chrome ore, with intervals of 10%, on their physical properties was studied. The phase equilibrium data were calculated using the phase relationships within the system M-M₂S-CMS-MR (M=MgO, S=SiO₂, C=CaO, R=R₂O₃). A computerized electron-probe microanalyser was applied to study the microstructure as well as microchemistry of the fired magnesite-chromite co-clinkers. Some physical and technological properties of the co-clinkered briquettes were also investigated by determining densification parameters, spalling resistance and load-bearing capacity.It is concluded that dense, spalling resistant and refractory magnesite, magnesite-chrome and chrome-magnesite refractories could be produced by co-clinkering of magnesite-chromite batches of 1000, 7030 and 3070 weight ratios, respectively, at 1600 °C. The prepared co-clinkers were subsequently graded, moulded and refired up to 1700 °C in order to obtain direct-bonded bricks. Meanwhile, dense chromite refractories with lower refractory quality could be processed by firing the Egyptian chrome ore up to 1600 °C.     

Hydrodynamic characteristics of magnetically fluidized beds consisting of a mixture of magnetic and nonmagnetic materials

The velocity of the beginning of fluidization and the porosity of a bed were investigated for a mixture of cast-iron ( _p = 1.086 mm) and copper ( _p = 1.086 mm) particles fluidized in a homogeneous external magnetic field of an intensity of up to 5662 A/m. By analyzing the forces that act on the magnetic particles the authors obtained an expression for calculating U_mb in a bed consisting of a mixture of magnetic and nonmagnetic particles. The calculation results are compared with the experimental data.     

Manufacturing of lightweight aggregates with carbon fiber and mineral wastes

The use of carbon fiber wastes (FC) as a component to manufacture lightweight aggregates (LWAs) for concrete has been studied. Amounts of 0, 2.5, 5 and 10% (w/w) of powdered FC were added into a mineral matrix composed by 90% of granite-marble sludge (COR) plus 10% of sepiolite rejection (SEP). The mixtures were milled, kneaded with water, extruded, shaped into pellets, oven-dried and finally fired at 1100, 1125 and 1150 °C for 4, 8 and 16 min in a rotary kiln. The main technological properties of the sintered aggregates were measured. The addition of FC promoted bloating and the formation of an internal structure in which both pores and unburnt carbon fibers were present. Improvements in lightness and mechanical properties were also observed. This is the first time that carbon fibers have been embedded within aggregates, opening the way to the development of a new type of LWAs for concrete.     

Rapid nondestructive on-site screening of methylamphetamine seizures by attenuated total reflection fourier transform infrared spectroscopy

The identification and quantification of illicit substances in the field is often desirable. Fourier transform infrared spectroscopy (FT-IR) has both qualitative and quantitative capabilities and field portable instruments are commercially available. Transmission infrared spectra of mixtures containing ephedrine hydrochloride, glucose, and caffeine and attenuated total reflection (ATR) infrared spectra of mixtures composed of methylamphetamine hydrochloride, glucose, and caffeine were used to develop principal component regression (PCR) calibration models. The root mean sum of errors of predictions (RMSEP) of all individual components in a mixture from a single measurement was <6% w/w, which reduced to approximately 3% w/w when triplicates were averaged. Sample mixing and grinding are essential to minimize the effect of heterogeneity, as deviations of up to 20% w/w were observed for single measurements of unground samples. Poor predictions of the components in a mixture occurred when samples were "contaminated" with substances not present in the calibration set, as would be expected. When only a single analyte (drug) was targeted, using a calibration set that contained both contaminated and uncontaminated samples, an RMSEP of approximately 4% w/w was achieved. The results demonstrate that ATR-FT-IR has the potential to quantify methylamphetamine samples, and possibly other licit or illicit substances, in at-seizure and on-site scenarios.     

Effects of glycerol and sorbitol on optical,mechanical, and gas barrier properties of potato peel‐based films

Potato peel is a by‐product of potato‐based food production and seen as a zero‐ or negative‐value waste of which millions of tons are produced every year. Previous studies showed that potato peel is a potential material for film development when plasticized with 10% to 50% glycerol (w/w potato peel). To further investigate potato peel as a film‐forming material, potato peel‐based films containing the plasticizer sorbitol were prepared and investigated on their physicochemical properties in addition to films containing glycerol. Due to sufficient producibility and handling of casted films in preliminary trials, potato peel‐based films containing 50%, 60%, or 70% glycerol (w/w potato peel) and films containing 90%, 100%, or 110% sorbitol (w/w potato peel) were prepared in this study. Generally, with increasing plasticizer concentration, water vapor and oxygen permeability of the films increased. Films containing glycerol showed higher water vapor and oxygen permeabilities than films containing sorbitol. Young's modulus, tensile strength, and elongation at break decreased with increasing sorbitol concentration, whereas no significant effect of plasticizer content on elongation at break was shown in films containing glycerol. Due to crystallization of films containing sorbitol as a plasticizer, potato peel‐based films containing 50% glycerol (w/w) were identified as the most promising films, characterized by a water vapor transmission rate of 268 g 100 μm m^?2 d^?1 and an oxygen permeability of 4 cm³ 100 μm m^?2 d^?1 bar^?1. Therefore, potato peel‐based cast films in this study showed comparable tensile properties with those of potato starch‐based films, comparable water vapor barrier with those of whey protein‐based films, and comparable oxygen barrier with those of polyamide films.     

Comparison of the relative stability of pharmaceutical cocrystals consisting of paracetamol and dicarboxylic acids

Objective: The aim of this study is to evaluate the relative stability of pharmaceutical cocrystals consisting of paracetamol (APAP) and oxalic acid (OXA) or maleic acid (MLA).

Significance: These observations of cocrystal stability under various conditions are useful coformer criteria when cocrystals are selected as the active pharmaceutical ingredient in drug development.

Method: The relative stability was determined from the preferentially formed cocrystals under various conditions.

Result: Cocrystal of APAP–OXA was more stable than that of APAP–MLA in a ternary cogrinding system and possessed thermodynamical stability. On the other hand, when grinding with moisture or maintaining at high temperatures and relative humidity conditions, APAP–MLA was more stable, and OXA converted to OXA dihydrate. In the slurry method, APAP–OXA was more stable in aprotic solvents because the APAP–OXA with low-solubility product precipitated.

Conclusions: The relative stability order was affected by preparing conditions of presence of moisture. This order might attribute to the small difference of crystal structure in the extension of the hydrogen bond network.     

Preparation and characterization of gelatin sponge millispheres from air-in-water-in-oil-type emulsions

A novel method for the preparation of gelatin sponge millispheres (GSMs) for biomaterials such as embolic agents and cell scaffolds was developed using an air-in-water-in-oil-type emulsion. The droplets, consisting of a foamy gelatin suspension in caprylic triglyceride, were gelled and rinsed with isopropanol. Sonication and depressurization were used during the rinsing process to create interconnected pores. GSMs cross-links created over 4 h at 155°C without any agent were insoluble and had short and long diameters of 1.1 ± 0.2 mm and 1.3 ± 0.2 mm, respectively. The residual isopropanol and caprylic triglyceride were <0.05% (w/w) and <1% (w/w) respectively. The level of bacterial endotoxins in the extracts was below 0.025 EU/ml, and no bacterial or fungal growth was found during sterility testing. The GSMs produced using this method were considered to meet the basic requirements of embolic agents.     

Development and evaluation of pluronic- and methylcellulose-based thermoreversible drug delivery system for insulin

The objective of the current work was to develop and evaluate thermoreversible subcutaneous drug delivery system for Insulin. Thermoreversible in-situ gel system was developed and evaluated both in-vitro and in-vivo comprising of pluronic F-127 alone or in combination with methylcellulose in different ratios. The drug release kinetics and mechanism was predicted by applying various mathematical models to the in-vitro dissolution data. Rabbits were used as animal model following subcutaneous injection to predict various pharmacokinetic parameters by applying Pk-Summit® software. The in-vitro and in-vivo data revealed that the formulation IPM 15/3 consisting of the pluronic F-127 (15% w/v) and methylcellulose (3% w/v) was the most robust and capable formulation for extending the drug release and maintaining basal plasma insulin level between 10 and 40?µU/ml for 240?h (10?d).     

Identification of technological knowledge intermediaries

Intermediaries in a technological knowledge network have recently been highlighted as crucial innovation drivers that accelerate technological knowledge flows. Although the patent network analysis has been frequently used to monitor technological knowledge structures, it has examined only sources or recipients of the technological knowledge by mainly estimating technological knowledge inflows or outflows of a network node. This study, therefore, aims to identify technological knowledge intermediaries when a technology-level knowledge network is composed of several industries. First, types of technological knowledge flows are deductively classified into four types by highlighting industry affiliations of source technologies and recipient technologies. Second, a directed technological knowledge network is generated at the technology class level, using patent co-classification analysis. Third, for each class, mediating scores are measured according to the four types. The empirical analysis illustrates the Korea’s technological knowledge network between 2000 and 2008. As a result, the four types of mediating scores are compared between industries, and industry-wise technological knowledge intermediaries are identified. The proposed approach is practical to explore converging processes in technology development where technology classes act as technological knowledge intermediaries among diverse industries.