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1.
The nanogranular nature of C-S-H 总被引:6,自引:0,他引:6
Despite its ubiquitous presence as binding phase in all cementitious materials, the mechanical behavior of calcium-silicate-hydrates (C-S-H) is still an enigma that has deceived many decoding attempts from experimental and theoretical sides. In this paper, we propose and validate a new technique and experimental protocol to rationally assess the nanomechanical behavior of C-S-H based on a statistical analysis of hundreds of nanoindentation tests. By means of this grid indentation technique we identify in situ two structurally distinct but compositionally similar C-S-H phases heretofore hypothesized to exist as low density (LD) C-S-H and high density (HD) C-S-H, or outer and inner products. The main finding of this paper is that both phases exhibit a unique nanogranular behavior which is driven by particle-to-particle contact forces rather than by mineral properties. We argue that this nanomechanical blueprint of material invariant behavior of C-S-H is a consequence of the hydration reactions during which precipitating C-S-H nanoparticles percolate generating contact surfaces. As hydration proceeds, these nanoparticles pack closer to center on-average around two characteristic limit packing densities, the random packing limit (η=64%) and the ordered face-centered cubic (fcc) or hexagonal close-packed (hcp) packing limit (η=74%), forming a characteristic LD C-S-H and HD C-S-H phase. 相似文献
2.
Constantinides CP Koutentis PA Schatz J 《Journal of the American Chemical Society》2004,126(49):16232-16241
Unrestricted density functional calculations in combination with the broken-symmetry approach and spin-projection methods have been employed to study a series of formally 4n pi antiaromatic linear and angular polyheteroacenes. Calculations show that the linear polyheteroacene molecules have either stable singlet zwitterionic 6-9 or singlet diradical 5 ground states because they sacrifice the aromaticity of the central arene to form two independent cyanines. The corresponding angular compounds 10-14 have robust triplet states, since they cannot create independent cyanines to escape their overall antiaromaticity. An analysis based on the SOMO-SOMO energy splittings, their spatial distributions, and the spin density populations for the triplet states is presented to clarify the factors that determine their ground state multiplicities. 相似文献
3.
Macomber RS Constantinides I Bauer JK Smith G Button A Lindstrom DO 《The Journal of organic chemistry》1996,61(2):727-734
The reaction of the title diketone (3) with phenyl Grignard produces (with rate constant k(1)) the conjugate base (6-M) of 10-hydroxy-10-phenylcyclooctadecanone (6), which is subsequently converted (with rate constant k(2)) to the conjugate base of the title diol, as a mixture of the cis (7, 55%) and trans (8, 45%) isomers. The ratio k(2)/k(1), 2.2 +/- 0.4, indicates that the carbonyl group in 6-M is 4.4 times as reactive as each carbonyl in 3. Competition experiments further demonstrate that the relative rates (per carbonyl) for addition of phenylmagnesium bromide to 3, 10-methylenecyclooctadecanone (11), and cyclopentadecanone (12) are 1.0:0.60:1.92. Possible reasons for this order of reactivity are discussed. Diols 7 and 8 undergo facile double dehydration to form the title diene 13, which is predicted by molecular mechanics calculations to be the most stable of the four possible symmetrical diene isomers. The structures of 7, 8, and 13 were secured by single-crystal X-ray studies. 相似文献
4.
The phase configuration of trapped internal waves from a body moving in a thermocline 总被引:1,自引:0,他引:1
Some two-dimensional internal wave systems are generated experimentally by a cylinder moving with constant velocity in a thermocline modelled with stratified brine. The phase configuration of the waves is shown to compare quite well with ray theory, and the phase changes which result from energy reflections are well defined in some of the schlieren photographs. 相似文献
5.
Alberola A Carter E Constantinides CP Eisler DJ Murphy DM Rawson JM 《Chemical communications (Cambridge, England)》2011,47(9):2532-2534
The β-sheet structure associated with chlorinated aromatics (d(Cl···Cl)≈ 4.0 ?) has been implemented to drive formation of π-stacked structures of dithiadiazolyl radicals. Both title compounds exhibit an increase in paramagnetism above 150 K but solid-state EPR studies indicate that the origin of the paramagnetism in these two systems is different. 相似文献
6.
Constantinides CP Koutentis PA Rawson JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(23):7109-7116
X-ray studies show that 1,3-diphenyl-7-(thien-2-yl)-1,4-dihydro-1,2,4-benzotriazin-4-yl (6) adopts a distorted, slipped π-stacked structure of centrosymmetric dimers with alternate short and long interplanar distances (3.48 and 3.52 ?). Cyclic voltammograms of 7-(thien-2-yl)benzotriazin-4-yl 6 show two fully reversible waves that correspond to the -1/0 and 0/+1 processes. EPR and DFT studies on radical 6 indicate that the spin density is mainly delocalized over the triazinyl fragment. Magnetic susceptibility measurements show that radical 6 obeys Curie-Weiss behavior in the 5-300 K region with C=0.378 emu K mol(-1) and θ=+4.72 K, which is consistent with ferromagnetic interactions between S=1/2 radicals. Fitting the magnetic susceptibility revealed the behavior is consistent with an alternating ferromagnetic chain (g=2.0071, J(1) =+7.12 cm(-1), J(2) =+1.28 cm(-1)). 相似文献
7.
Christos P. Constantinides Dr. Panayiotis A. Koutentis Prof. Jeremy M. Rawson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(48):15433-15438
7‐(4‐Fluorophenyl) and 7‐phenyl‐substituted 1,3‐diphenyl‐1,4‐dihydro‐1,2,4‐benzotriazin‐4‐yl radicals were characterized by X‐ray diffraction analysis and variable‐temperature magnetic susceptibility studies. The radicals pack in 1D π stacks of equally spaced slipped radicals with interplanar distances of 3.59 and 3.67 Å and longitudinal angles of 40.97 and 43.47°, respectively. Magnetic‐susceptibility studies showed that both radicals exhibit antiferromagnetic interactions. Fitting the magnetic data revealed that the behavior is consistent with 1D regular linear antiferromagnetic chain with J=?12.9 cm?1, zJ′=?0.4 cm?1, g=2.0069 and J=?11.8 cm?1, zJ′=?6.5 cm?1, g=2.0071, respectively. Magnetic‐exchange interactions in benzotriazinyl radicals are sensitive to the degree of slippage, and inter‐radical separation and subtle changes in structure alter the fine balance between ferro‐ and antiferromagnetic interactions. 相似文献
8.
A computer-aided simulator of immiscible displacement in strongly water-wet consolidated porous media that takes into account the effects of the wetting films is developed. The porous medium is modeled as a three-dimensional network of randomly sized unit cells of the constricted-tube type. Precursor wetting films are assumed to advance through the microroughness of the pore walls. Two types of pore wall microroughness are considered. In the first type of microroughness, the film advances quickly, driven by capillary pressure. In the second type, the meniscus moves relatively slowly, driven by local bulk pressure differences. In the latter case, the wetting film often forms a collar that squeezes the thread of oil causing oil disconnection. Each pore is assumed to have either one of the aforementioned microroughness types, or both. The type of microroughness in each pore is assigned randomly. The simulator is used to predict the residual oil saturation as a function of the pertinent parameters (capillary number, viscosity ratio, fraction of pores with each type of wall microroughness). These results are compared with those obtained in the absence of wetting films. It is found that wetting films cause substantial increase of the residual oil saturation. Furthermore, the action of the wetting films causes an increase of the mean volume of the residual oil ganglia. 相似文献
9.
Multianalytical Study of Patina Formed on Archaeological Metal Objects from Bliesbruck-Reinheim 总被引:1,自引:0,他引:1
Michael Wadsak Ina Constantinides Guido Vittiglio Annemie Adriaens Koen Janssens Manfred Schreiner Freddy C. Adams Philippe Brunella Michel Wuttmann 《Mikrochimica acta》2000,133(1-4):159-164
Patinas naturally formed on archaeological bronze alloys were characterized using light microscopy (LM), micro energy dispersive
X-ray fluorescence analysis (μ-EDXRF), time of flight secondary ion mass spectrometry (TOF-SIMS) and scanning electron microscopy
in combination with energy dispersive X-ray microanalysis (SEM/EDX). The examinations carried out on cross-sections of samples
have shown that in all samples the copper content in the corrosion layer is lower than in the bulk, while an increase of tin
and lead could be observed. Two different types of corrosion were found: first type, a corrosion formation leading to a three
layer structure was observed on lead bronze. The outer layer consists mainly of Cu(II) compounds and soil material, followed
by a fragmented layer of cuprous oxide and the surface layer of the alloy, where a depletion of copper and an enrichment of
tin and high amounts of Cl could be detected. The second type of corrosion is characterized by a two layer structure on the
tin bronze sample consisting of an outer layer with copper containing corrosion products and a layer with cracks, which reveals
a depletion of copper whereas tin and lead are enriched. Also high amounts of Si were detected in this surface layer. 相似文献
10.