scholarly journals A Tale of Two Transitions: Unraveling Two Distinct Polymorph Transition Mechanisms in One n-Type Single Crystal for Dynamic Electronics

2021 ◽  
Author(s):  
Daniel W. Davies ◽  
Sang Kyu Park ◽  
Stephen B. Shiring ◽  
Hyunjoong Chung ◽  
Prapti Kafle ◽  
...  
Keyword(s):  
Single Crystal ◽  
Growth Mechanism ◽  
High Performance ◽  
Electron Paramagnetic Resonance Spectroscopy ◽  
Nucleation And Growth ◽  
The Other ◽  
Resonance Spectroscopy ◽  
Other Hand ◽  
Nucleation And Growth Mechanism

Cooperativity is used by living systems to circumvent energetic and entropic barriers to yield highly efficient molecular processes. Cooperative structural transitions involve the simultaneous, concerted displacement of molecules in a crystalline material, in stark contrast to the more typical molecule-by-molecule nucleation and growth mechanism often breaking the single crystallinity. Cooperative transitions have acquired much attention in the research community for their low transition barriers, ultrafast kinetics, and structural reversibility. On the other hand, cooperative transitions are rarely observed in molecular crystals and the molecular origin is not well understood. Single crystals of 2-dimensional quinoidal terthiophene (2DQTT-o-B), a high-performance n-type organic semiconductor, demonstrate two thermally-activated, reversible phase transitions with one exhibiting a cooperative mechanism and the second exhibiting a nucleation and growth mechanism. In situ microscopy, single crystal and grazing incidence X-ray diffraction (GIXD), along with Raman spectroscopy suggest a reorientation of the alkyl side chains results in a cooperative transition behavior. On the other hand, the nucleation and growth transition is coincident with both side chain melting and the emergence of new spin-spin interactions between conjugated cores, confirmed through in situ electron paramagnetic resonance spectroscopy (EPR). This is the first observation of biradical interactions directly initiating a structural transition. Through studying these fundamental mechanisms, we establish alkyl chain conformation and disorder as integral to rationally controlling these polymorphic behaviors for novel electronic applications.

Electrochemical Growth of Single-Crystal Metal Nanowires via a Two-Dimensional Nucleation and Growth Mechanism

Nano Letters ◽  
2003 ◽  
Vol 3 (7) ◽  
pp. 919-923 ◽  
Author(s):  
Mingliang Tian ◽  
Jinguo Wang ◽  
James Kurtz ◽  
Thomas E. Mallouk ◽  
M. H. W. Chan
Keyword(s):  
Single Crystal ◽  
Growth Mechanism ◽  
Nucleation And Growth ◽  
Metal Nanowires ◽  
Two Dimensional ◽  
Electrochemical Growth ◽  
Nucleation And Growth Mechanism

Formation of coherent twins in YBa2Cu3O7–δ superconductors

1989 ◽  
Vol 4 (4) ◽  
pp. 795-801 ◽  
Author(s):  
C. J. Jou ◽  
J. Washburn
Keyword(s):  
Oxygen Uptake ◽  
Growth Mechanism ◽  
Oxygen Uptake Rate ◽  
Nucleation And Growth ◽  
Electron Microscopic ◽  
Transmission Electron ◽  
Transmission Electron Microscopic ◽  
Twin Formation ◽  
Boundary Model ◽  
Nucleation And Growth Mechanism

A nucleation-and-growth mechanism for the twin formation in YBa2Cu3O7–δ superconductors based on the oxygen uptake rate curve and published transmission electron microscopic observations is proposed together with an oxygen-depleted twin boundary model. The difficulty of reaching stoichiometric YBa2Cu3O7 is explained.

scholarly journals Ambient base-free glycerol oxidation over bimetallic PdFe/SiO2 by in situ generated active oxygen species

2021 ◽  
Author(s):  
Ricci Underhill ◽  
Mark Douthwaite ◽  
Richard J. Lewis ◽  
Peter J. Miedziak ◽  
Robert D. Armstrong ◽  
...  
Keyword(s):  
Heterogeneous Catalysts ◽  
Bimetallic Catalyst ◽  
Electron Paramagnetic Resonance Spectroscopy ◽  
Active Oxygen Species ◽  
Catalytic Performance ◽  
Resonance Spectroscopy ◽  
Oxygen Species ◽  
Paramagnetic Resonance ◽  
Temperature Oxidation

AbstractLow temperature oxidation of alcohols over heterogeneous catalysts is exceptionally challenging, particularly under neutral conditions. Herein, we report on an efficient, base-free method to oxidise glycerol over a 0.5%Pd-0.5%Fe/SiO2 catalyst at ambient temperature in the presence of gaseous H2 and O2. The exceptional catalytic performance was attributed to the in situ formation of highly reactive surface-bound oxygenated species, which promote the dehydrogenation on the alcohol. The PdFe bimetallic catalyst was determined to be significantly more active than corresponding monometallic analogues, highlighting the important role both metals have in this oxidative transformation. Fe leaching was confirmed to occur over the course of the reaction but sequestering experiments, involving the addition of bare carbon to the reactions, confirmed that the reaction was predominantly heterogeneous in nature. Investigations with electron paramagnetic resonance spectroscopy suggested that the reactivity in the early stages was mediated by surface-bound reactive oxygen species; no homogeneous radical species were observed in solution. This theory was further evidenced by a direct H2O2 synthesis study, which confirmed that the presence of Fe in the bimetallic catalyst neither improved the synthesis of H2O2 nor promoted its decomposition over the PdFe/SiO2 catalyst.

Did Ground Cover Change Over Geologic Time?

2000 ◽  
Vol 6 ◽  
pp. 171-182 ◽  
Author(s):  
Ben A. LePage ◽  
Hermann W. Pfefferkorn
Keyword(s):  
Fossil Record ◽  
Ground Cover ◽  
The Other ◽  
Detailed Account ◽  
Geologic Time ◽  
The Past ◽  
Other Hand ◽  
Plant Fossil

When one hears the term “ground cover,” one immediately thinks of “grasses.” This perception is so deep-seated that paleobotanists even have been overheard to proclaim that “there was no ground cover before grasses.” Today grasses are so predominant in many environments that this perception is perpetuated easily. On the other hand, it is difficult to imagine the absence or lack of ground cover prior to the mid-Tertiary. We tested the hypothesis that different forms of ground cover existed in the past against examples from the Recent and the fossil record (Table 1). The Recent data were obtained from a large number of sources including those in the ecological, horticultural, and microbiological literature. Other data were derived from our knowledge of Precambrian life, sedimentology and paleosols, and the plant fossil record, especially in situ floras and fossil “monocultures.” Some of the data are original observations, but many others are from the literature. A detailed account of these results will be presented elsewhere (Pfefferkorn and LePage, in preparation).

On the Chemistry of Tetrabenzyl Thiuram Disulfide and Tetramethyl Thiuram Disulfide with Bis (Triethoxysilylpropyl) Tetrasulfide in Silica Compounds

2003 ◽  
Vol 76 (4) ◽  
pp. 876-891 ◽  
Author(s):  
R. N. Datta ◽  
A. G. Talma ◽  
S. Datta ◽  
P. G. J. Nieuwenhuis ◽  
W. J. Nijenhuis ◽  
...  
Keyword(s):  
High Performance ◽  
Room Temperature ◽  
Succinic Anhydride ◽  
Dynamic Properties ◽  
The Other ◽  
Resonance Spectroscopy ◽  
Reaction Products ◽  
Negative Effect ◽  
Higher Temperature ◽  
Analytical Tools

Abstract The use of thiurams such as Tetramethyl thiuram disulfide (TMTD) or Tetrabenzyl thiuram disulfide (TBzTD) has been explored to achieve higher cure efficiency. The studies suggest that a clear difference exists between the effect of TMTD versus TBzTD. TMTD reacts with Bis (triethoxysilylpropyl) tetrasulfide (TESPT) and this reaction can take place even at room temperature. On the other hand, the reaction of TBzTD with TESPT is slow and takes place only at higher temperature. High Performance Liquid Chromatography (HPLC) with mass (MS) detection, Nuclear Magnetic Resonance Spectroscopy (NMR) and other analytical tools have been used to understand the differences between the reaction of TMTD and TESPT versus TBzTD and TESPT. The reaction products originating from these reactions are also identified. These studies indicate that unlike TMTD, TBzTD improves the cure efficiency allowing faster cure without significant effect on processing characteristics as well as dynamic properties. The loading of TESPT is reduced in a typical Green tire compound and the negative effect on viscosity is repaired by addition of anhydrides, such as succinic anhydride, maleic anhydride, etc.

Sign in / Sign up

Export Citation Format

Share Document