scholarly journals Engineering micromechanics of soft porous crystals for negative gas adsorption

2020 ◽  
Vol 11 (35) ◽  
pp. 9468-9479 ◽  
Author(s):  
Simon Krause ◽  
Jack D. Evans ◽  
Volodymyr Bon ◽  
Irena Senkovska ◽  
Sebastian Ehrling ◽  
...  
Keyword(s):  
Mechanical Properties ◽  
Elastic Properties ◽  
Gas Adsorption ◽  
Building Blocks ◽  
Molecular Building Blocks

We characterise the elastic properties of molecular building blocks and how they impact the mechanical properties of soft porous crystals.

scholarly journals Engineering Micromechanics of Soft Porous Crystals for Negative Gas Adsorption

2020 ◽  
Author(s):  
Simon Krause ◽  
Jack D. Evans ◽  
Volodymyr Bon ◽  
Irena Senkovska ◽  
Sebastian Ehrling ◽  
...  
Keyword(s):  
Yield Stress ◽  
Mechanical Response ◽  
Gas Adsorption ◽  
Molecular Level ◽  
Nitrogen Adsorption ◽  
Building Blocks ◽  
Activation Barriers ◽  
Framework Materials ◽  
Dynamic Framework ◽  
Molecular Building Blocks

Framework materials at the molecular level, such as metal-organic frameworks (MOF), were recently found to exhibit exotic and counterintuitive micromechanical properties. Stimulated by host-guest interactions, these so-called soft porous crystals can display counterintuitive adsorption phenomena such as negative gas adsorption (NGA). NGA materials are bistable frameworks where the occurrence of a metastable overloaded state leads to pressure amplification upon a sudden framework contraction. How can we control activation barriers and energetics via functionalization of the molecular building blocks that dictate the frameworks’ 30 mechanical response? In this work we tune the elastic and inelastic properties of building blocks at the 31 molecular level and analyze the mechanical response of the resulting frameworks. From a set of 11 frameworks, we demonstrate that widening of the backbone increases elasticity, while elongation of the building blocks results in a decrease in critical yield stress of buckling. We further functionalize the backbone by incorporation of sp3 hybridized carbon atoms to soften the molecular building blocks, or stiffen them with sp2 and sp carbons. Computational modeling shows how these modifications of the building blocks tune the 36 activation barriers within the energy landscape of the guest-free bistable frameworks. Only frameworks with free energy barriers in the range of 800 to 1100 kJ mol–1 37 per unit cell, and moderate yield stress of 0.6 to 38 1.2 nN for single ligand buckling, exhibit adsorption-induced contraction and negative gas adsorption. Advanced experimental in situ methodologies give detailed insights into the structural transitions and the adsorption behavior. The new framework DUT-160 shows the highest magnitude of NGA ever observed for nitrogen adsorption at 77 K. Our computational and experimental analysis of the energetics and mechanical response functions of porous frameworks is an important step towards tuning activation barriers in dynamic framework materials and provides critical design principles for molecular building blocks leading to pressure amplifying materials<br>

scholarly journals Engineering Micromechanics of Soft Porous Crystals for Negative Gas Adsorption

2020 ◽  
Author(s):  
Simon Krause ◽  
Jack D. Evans ◽  
Volodymyr Bon ◽  
Irena Senkovska ◽  
Sebastian Ehrling ◽  
...  
Keyword(s):  
Yield Stress ◽  
Mechanical Response ◽  
Gas Adsorption ◽  
Molecular Level ◽  
Nitrogen Adsorption ◽  
Building Blocks ◽  
Activation Barriers ◽  
Framework Materials ◽  
Dynamic Framework ◽  
Molecular Building Blocks

Framework materials at the molecular level, such as metal-organic frameworks (MOF), were recently found to exhibit exotic and counterintuitive micromechanical properties. Stimulated by host-guest interactions, these so-called soft porous crystals can display counterintuitive adsorption phenomena such as negative gas adsorption (NGA). NGA materials are bistable frameworks where the occurrence of a metastable overloaded state leads to pressure amplification upon a sudden framework contraction. How can we control activation barriers and energetics via functionalization of the molecular building blocks that dictate the frameworks’ 30 mechanical response? In this work we tune the elastic and inelastic properties of building blocks at the 31 molecular level and analyze the mechanical response of the resulting frameworks. From a set of 11 frameworks, we demonstrate that widening of the backbone increases elasticity, while elongation of the building blocks results in a decrease in critical yield stress of buckling. We further functionalize the backbone by incorporation of sp3 hybridized carbon atoms to soften the molecular building blocks, or stiffen them with sp2 and sp carbons. Computational modeling shows how these modifications of the building blocks tune the 36 activation barriers within the energy landscape of the guest-free bistable frameworks. Only frameworks with free energy barriers in the range of 800 to 1100 kJ mol–1 37 per unit cell, and moderate yield stress of 0.6 to 38 1.2 nN for single ligand buckling, exhibit adsorption-induced contraction and negative gas adsorption. Advanced experimental in situ methodologies give detailed insights into the structural transitions and the adsorption behavior. The new framework DUT-160 shows the highest magnitude of NGA ever observed for nitrogen adsorption at 77 K. Our computational and experimental analysis of the energetics and mechanical response functions of porous frameworks is an important step towards tuning activation barriers in dynamic framework materials and provides critical design principles for molecular building blocks leading to pressure amplifying materials<br>

A First Principles Approach for Partitioning Linear Response Properties into Additive and Cooperative Contributions

2018 ◽  
Author(s):  
Daniel Lambrecht ◽  
Eric Berquist
Keyword(s):  
First Principles ◽  
Linear Response ◽  
Building Blocks ◽  
Field Method ◽  
Response Property ◽  
Response Properties ◽  
Consistent Field ◽  
Molecular Building Blocks ◽  
Self Consistent ◽  
Self Consistent Field

We present a first principles approach for decomposing molecular linear response properties into orthogonal (additive) plus non-orthogonal/cooperative contributions. This approach enables one to 1) identify the contributions of molecular building blocks like functional groups or monomer units to a given response property and 2) quantify cooperativity between these contributions. In analogy to the self consistent field method for molecular interactions, SCF(MI), we term our approach LR(MI). The theory, implementation and pilot data are described in detail in the manuscript and supporting information.

A new molecular building blocks: Synthesis, crystal structure, magnetic and spectroscopic properties of Cu(II) and Ni(II) macrocyclic complexes

Polyhedron ◽  
2011 ◽  
Vol 30 (15) ◽  
pp. 2550-2557 ◽  
Author(s):  
Katarzyna Suracka ◽  
Alina Bieńko ◽  
Jerzy Mroziński ◽  
Rafał Kruszyński ◽  
Dariusz Bieńko ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Building Blocks ◽  
Spectroscopic Properties ◽  
Macrocyclic Complexes ◽  
Molecular Building Blocks

scholarly journals Acid-Catalysed Liquid-to-Solid Transitioning of Arylazoisoxazole Photoswitches

2021 ◽  
Author(s):  
Luuk Kortekaas ◽  
Julian Simke ◽  
Niklas Arndt ◽  
Marcus Böckmann ◽  
Nikos Doltsinis ◽  
...  
Keyword(s):  
Building Blocks ◽  
Vital Role ◽  
Responsive Materials ◽  
Molecular Building Blocks ◽  
Physical Changes

Molecular photoswitches play a vital role in the development of responsive materials. These molecular building blocks are particularly attractive when multiple stimuli can be combined to bring about physical changes,...

scholarly journals Mechanical properties of zirconium alloys and zirconium hydrides predicted from density functional perturbation theory

2015 ◽  
Vol 44 (43) ◽  
pp. 18769-18779 ◽  
Author(s):  
Philippe F. Weck ◽  
Eunja Kim ◽  
Veena Tikare ◽  
John A. Mitchell
Keyword(s):  
Mechanical Properties ◽  
Perturbation Theory ◽  
Elastic Properties ◽  
Density Functional ◽  
Mechanical Stability ◽  
Zirconium Alloys ◽  
Density Functional Perturbation Theory ◽  
Zirconium Hydrides

The elastic properties and mechanical stability of zirconium alloys and zirconium hydrides have been investigated within the framework of density functional perturbation theory. Results show that the lowest-energy Pn3̄m δ-ZrH1.5 phase is not mechanically stable.

Mechanical properties of nickel beryllides

1989 ◽  
Vol 4 (6) ◽  
pp. 1347-1353 ◽  
Author(s):  
T. G. Nieh ◽  
J. Wadsworth ◽  
C. T. Liu
Keyword(s):  
Crystal Structure ◽  
Mechanical Properties ◽  
Elastic Properties ◽  
Room Temperature ◽  
Vickers Microhardness ◽  
Interstitial Oxygen ◽  
Equiatomic Composition ◽  
Room Temperature Ductility ◽  
Hardness Increase ◽  
Microhardness Tester

The elastic properties of nickel beryllide have been evaluated from room temperature to 1000 °C. The room temperature modulus is measured to be 186 GPa, which is relatively low by comparison with other B2 aluminides such as NiAl and CoAl. Hardness measurements were carried out on specimens that had compositions over the range from 49 to 54 at. % Be, using both a Vickers microhardness tester and a nanoindentor. It was found that the hardness of NiBe exhibits a minimum at the equiatomic composition. This behavior is similar to that of aluminides of the same crystal structure, e.g., NiAl and CoAl. The effect of interstitial oxygen on the hardness of NiBe has also been studied and the results show that the presence of oxygen in NiBe can cause a significant increase in hardness. It is demonstrated that the hardness increase for the off-stoichiometric compositions is primarily caused by interstitial oxygen and can only be attributed partially to anti-site defects generated in off-stoichiometric compositions. Nickel beryllides appear to have some intrinsic room temperature ductility, as evidenced by the absence of cracking near hardness indentations.

A Molecular Artisans Guide to Supramolecular Coordination Complexes and Metal Organic Frameworks

2015 ◽  
Vol 03 (01n02) ◽  
pp. 1540004 ◽  
Author(s):  
Xialu Wu ◽  
David J. Young ◽  
T. S. Andy Hor
Keyword(s):  
Chemical Reactivity ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Coordination Complexes ◽  
Large Molecules ◽  
Molecular Building Blocks ◽  
Supramolecular Coordination ◽  
Metal Organic ◽  
Molecular Synthesis ◽  
And Function

As molecular synthesis advances, we are beginning to learn control of not only the chemical reactivity (and function) of molecules, but also of their interactions with other molecules. It is this basic idea that has led to the current explosion of supramolecular science and engineering. Parallel to this development, chemists have been actively pursuing the design of very large molecules using basic molecular building blocks. Herein, we review the general development of supramolecular chemistry and particularly of two new branches: supramolecular coordination complexes (SCCs) and metal organic frameworks (MOFs). These two fields are discussed in detail with typical examples to illustrate what is now possible and what challenges lie ahead for tomorrow's molecular artisans.

scholarly journals Recycled Mortars with Ceramic Aggregates. Pore Network Transmutation and Its Relationship with Physical and Mechanical Properties

Materials ◽  
2021 ◽  
Vol 14 (6) ◽  
pp. 1543
Author(s):  
Francisca Guadalupe Cabrera-Covarrubias ◽  
José Manuel Gómez-Soberón ◽  
Carlos Antonio Rosas-Casarez ◽  
Jorge Luis Almaral-Sánchez ◽  
Jesús Manuel Bernal-Camacho
Keyword(s):  
Mechanical Properties ◽  
Image Analysis ◽  
Open Porosity ◽  
Gas Adsorption ◽  
Physical And Mechanical Properties ◽  
Recycled Aggregate ◽  
Bet Surface Area ◽  
Sem Image ◽  
The Relationship ◽  
Sem Image Analysis

The porosity of mortars with recycled ceramic aggregates (10, 20, 30, 50, and 100% as a replacement of natural aggregate) was evaluated and analyzed using three different techniques. The results of gas adsorption (N2), Scanning Electron Microscopy (SEM) image analysis and open porosity allowed establishing the relationship between the recycled aggregate content and the porosity of these mortars, as well as the relationship between porosity and the physical and mechanical properties of the mortars: absorption, density, compressive strength, modulus of elasticity, and drying shrinkage. Using the R2 coefficient and the equation typology as criteria, additional data such as Brunauer, Emmett, and Teller (BET) surface area (N2 adsorption) established significant correlations with the mentioned properties; with SEM image analysis, no explanatory relationships could be established; and with open porosity, revealing relationships were established (R2 > 0.9). With the three techniques, it was confirmed that the increase in porosity is related to the increase in the amount of ceramic aggregate; in particular with gas adsorption (N2) and open porosity. It was concluded that the open porosity technique can explain the behavior of these recycled mortars with more reliable data, in a simple and direct way, linked to its establishment with a more representative sample of the mortar matrix.

Sign in / Sign up

Export Citation Format

Share Document