From the Understanding of the Reaction Mechanism Towards Optimizing the Deposition Rate and Optoelectronic Properties of a-Si:H

1989 ◽  
Vol 149 ◽  
Author(s):  
S. Veprek ◽  
M. Heintze ◽  
R. Bayer ◽  
N. Jurčik-Rajman
Keyword(s):  
Reaction Mechanism ◽  
Surface Coverage ◽  
Kinetic Studies ◽  
Reactive Intermediates ◽  
Sticking Coefficient ◽  
High Quality ◽  
Rate Determining Step ◽  
Homogeneous Good ◽  
Good Agreement

ABSTRACTWe present new results of kinetic studies of the deposition of high quality a-Si:H which strongly support the reaction mechanism suggested in our earlier papers: 1. SiH4 → SiH2; 2. SiH2 + SiS4 → Si2H6 (SiH2 + Si2H6 → Si3H6); 3. Si2H6 → 2a-Si:H (Si3H8 → 3a-Si:H). The “SiH3 mechanism”, as promoted by several workers, is in contradiction with these experimental facts.The di- and trisilane, which have a much higher reactive sticking coefficient than monosilane, play the role of reactive intermediates which facilitate the heterogeneous decomposition of silicon carrying species at the surface of the growing film. The values of the reactive sticking coefficient of Si2H6 and Si3H8 depend on the surface coverage by chemisorbed hydrogen; they increase with decreasing surface coverage. Under the conditions of the growth of high quality a-Si:H films the reactive sticking coefficient of disilane amounts to 10−4 to 10−2 which is in a good agreement with recent data of other authors.The rate determining step of the growth of high quality a-Si:H films is the desorption of hydrogen from the surface of the growing film. This can be strongly enhanced by ion bombardment at impact energy of <100 eV. In this way, homogeneous, good quality films were deposited at rates up to 1800 Angströms/min, and there is a well justified hope that this rate can be further increased.

The remarkable role of solvent in reaction mechanism studies by electrospray mass spectrometry

2015 ◽  
Vol 2 (8) ◽  
pp. 990-994 ◽  
Author(s):  
Hao-Yang Wang ◽  
Jun-Ting Zhang ◽  
Shu-Sheng Zhang ◽  
Yin-Long Guo
Keyword(s):  
Mass Spectrometry ◽  
Reaction Mechanism ◽  
Electrospray Mass Spectrometry ◽  
Reactive Intermediates ◽  
Role Of Solvent

The solvent assistance technologies in detecting reactive intermediates in complicated reaction solutions using electrospray mass spectrometry were summarized and discussed.

The Chemistry of Vulcanization. VIII. Role of Zinc Butyrate in the Reaction of Diphenylmethane, Sulfur and 2-Benzothiazolyl Disulfide

1961 ◽  
Vol 34 (2) ◽  
pp. 648-657
Author(s):  
Haruko Fukuda ◽  
Jitsuo Tsurugi
Keyword(s):  
Zinc Oxide ◽  
Reaction Mechanism ◽  
Butyric Acid ◽  
Rate Equation ◽  
Experimental Results ◽  
Zinc Salt ◽  
Elementary Sulfur ◽  
Rate Determining Step

Abstract Diphenylmethane (DPM) which contains α-methylenic hydrogen has been used as a model of rubber hydrocarbon, and reactions involving DPM, sulfur and thiazole type accelerators in the absence of zinc oxide or soap were reported in previous papers. These papers reported that 2-mercaptobenzothiazole (MBT), 2-benzothiazolyl disulfide (MBTS) and zinc salt of 2-mercaptobenzothiazole (ZMBT) generate the same radical, i.e., 2-benzothiazolesulfenyl which has the accelerating effect. This radical opens the ring of elementary sulfur and thus accelerates vulcanization since the spontaneous splitting of the sulfur ring molecule to a biradical was found to be the rate determining step in the reaction of DPM with sulfur alone. Processes by which accelerators generate this radical differ from each other owing to the types of accelerators, that is, mercaptan, disulfide and zinc mercaptide type. The previous paper reported the reaction involving DPM, sulfur and MBT in the presence of zinc butyrate. According to this, MBT first reacts with zinc butyrate to form butyric acid and ZMBT, the latter then generating the effective benzothiazole-sulfenyl radical. Thus, even in the presence of zinc soap, the essential mechanism of acceleration is the same as in the absence of zinc soap, though the process and rate for forming benzothiazolesulfenyl radical are different in the absence of zinc soap. In the present paper the reaction of DPM, sulfur and MBTS in the presence of zinc butyrate are reported. The reaction mechanism will be deduced from the experimental results obtained here and from conclusions obtained in the previous papers. The rate equation for MBTS consumption and equation for the accelerating efficiency for this accelerator are derived from the mechanism. The theoretical equations were examined by experiments.

Aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran on supported vanadium oxide catalysts: Structural effect and reaction mechanism

2011 ◽  
Vol 84 (3) ◽  
pp. 765-777 ◽  
Author(s):  
Junfang Nie ◽  
Haichao Liu
Keyword(s):  
Reaction Mechanism ◽  
Vanadium Oxide ◽  
Aerobic Oxidation ◽  
Kinetic Studies ◽  
Structural Effect ◽  
Monolayer Capacity ◽  
Rate Determining Step ◽  
Vis Spectroscopy ◽  
Wide Range ◽  
Support Surfaces

The structure–activity relationship and reaction mechanism for selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) in toluene were studied on vanadium oxide domains on TiO2, Al2O3, Nb2O5, ZrO2, and MgO and with a wide range of VOx surface densities. The structures of these catalysts were characterized by X-ray diffraction (XRD), diffuse reflectance UV–vis spectroscopy (UV–vis DRS), and Raman spectroscopy, and their reducibility was probed by H2-temperature programmed reduction. The structures of the VOx domains evolved from monovanadate to polyvanadate structures with increasing the VOx surface densities, and finally to crystalline V2O5 clusters at surface densities above one-monolayer capacity. Within one-monolayer capacity, higher VOx surface densities and more reducible supports led to higher reducibility and reactivity of the VOx domains. The support surfaces covered with polyvanadates and V2O5 clusters and the supports with acidity favored the formation of DFF. The correlation between the reducibility and reactivity, together with the kinetic studies, suggests that the HMF oxidation to DFF proceeds via the redox mechanism involving the V5+/V4+ redox cycles and the reoxidation of V4+ to V5+ by O2 as the rate-determining step. These results may provide guidance for the design of more efficient catalysts for the HMF oxidation to synthesize DFF.

Making Movies and Community of Talent

2019 ◽  
Vol 10 (11) ◽  
pp. 1057-1064
Author(s):  
Katsuhiko Hirasawa ◽  
Keyword(s):  
Shop Floor ◽  
High Quality ◽  
Democratic Leadership ◽  
Staff Members

Staff members at a movie company Daiei, known for presumably the world’s best film technology, continued to produce movies for several months even after the company went bankrupt. It was because they desired to make outstanding films. A director can create a high-quality film by combining the skills and ideas of such staff. Akira Kurosawa named the group that could produce excellent works the “Community of Talents”. By using research on a community as a clue, this paper aims to highlight how the “Community of Talents” is organized. First I point out that a “Community of Talents” is formulated primarily by the labor of the staff based on Kumazawa’s “Community on the Shop Floor”. The paper subsequently refers to research by Heinrich Nicklish, a representative researcher on the study of community in Germany, in an attempt to verify that the community is a group of people established on functions. Lastly, the paper explores Guido Fisher’s research to reveal the role of democratic leadership centered on the director who transforms the objectified staff in the organization into an independently-minded presence and help them prove their abilities. The paper continues to emphasize the significance of leadership in the formation of the “Community of Talents”.

Ligand-Enabled γ-C(sp3)–H Olefination of Free Carboxylic Acids

2020 ◽  
Author(s):  
Kiron Kumar Ghosh ◽  
Alexander Uttry ◽  
Francesca Ghiringhelli ◽  
Arup Mondal ◽  
Manuel van Gemmeren
Keyword(s):  
Reaction Mechanism ◽  
Carboxylic Acids ◽  
Michael Addition ◽  
Kinetic Studies ◽  
Wide Range ◽  
Palladium Catalyzed

We report the ligand enabled C(sp3)–H activation/olefination of free carboxylic acids in the γ-position. Through an intramolecular Michael-addition, δ-lactones are obtained as products. Two distinct ligand classes are identified that enable the challenging palladium-catalyzed activation of free carboxylic acids in the γ-position. The developed protocol features a wide range of acid substrates and olefin reaction partners and is shown to be applicable on a preparatively useful scale. Insights into the underlying reaction mechanism obtained through kinetic studies are reported.<br>

Full Kinetics and a Mechanism Investigation for the Generation of 4- Substituted 1, 4-Dihydropyridine Derivatives in the Presence of Green Catalyst and Aqueous Medium: Experimental Procedure

2020 ◽  
Vol 17 ◽  
Author(s):  
Sayyed Mostafa Habibi-Khorassani ◽  
Mehdi Shahraki ◽  
Sadegh Talaiefar
Keyword(s):  
Reaction Mechanism ◽  
Reaction Centre ◽  
Green Catalyst ◽  
Experimental Procedure ◽  
Dominant Mechanism ◽  
Rate Determining Step ◽  
12 Steps ◽  
Reaction Constant ◽  
Substituted 1 ◽  
Dihydropyridine Derivatives

Aims and Objective: The main objective of the kinetic investigation of the reaction among ethyl acetoacetate 1, ammoniumacetat 2, dimedone 3 and diverse substitutions of benzaldehyde 4-X, (X= H, NO2, CN, CF3, Cl, CH (CH3)2, CH3, OCH3, OCH3, and OH) for the generation of 4-substituted 1, 4-dihydropyridine derivatives (product 5) was the recognition of the most realistic reaction mechanism. The layout of the reaction mechanism studied kinetically by means of the UV-visible spectrophotometry approach. Materials and Methods: Among the various mechanisms, only mechanism1 (path1) involving 12 steps was recognized as a dominant mechanism (path1). Herein, the reaction between reactants 1 and 2 (kobs= 814.04 M-1 .min-1 ) and also compound 3 and 4-H (kobs= 151.18 M-1 .min-1 ) were the logical possibilities for the first and second fast steps (step1 and step2, respectively). Amongst the remaining steps, only step9 of the dominant mechanism (path1) had substituent groups (X) near the reaction centre that could be directly resonated with it. Results and Discussion: Para electron-withdrawing or donating groups on the compound 4-X increases the rate of the reaction 4 times more or decreases 8.7 times less than the benzaldehyde alone. So, this step is sensitive for monitoring any small or huge changes in the reaction rate. For this reason, step9 is the rate-determining step of the reaction mechanism (path1). Conclusion: The recent result is the agreement with the Hammett description with an excellent dual substituent factor (r = 0.990) and positive value of reaction constant (ρ = +0.9502) which confirmed both the resonance and inductive effects “altogether” contributed on the reaction centre of step9 in the dominant mechanism (path1).

When Do Auditors Use Specialists' Work to Improve Problem Representations of and Judgments about Complex Estimates?

2017 ◽  
Vol 93 (4) ◽  
pp. 177-202 ◽  
Author(s):  
Emily E. Griffith
Keyword(s):  
Pattern Recognition ◽  
Situational Factors ◽  
Situational Factor ◽  
High Quality ◽  
Quality Audit ◽  
Domain Specific ◽  
Epistemic Motivation ◽  
Specific Expertise ◽  
Problem Representations

ABSTRACT Auditors are more likely to identify misstatements in complex estimates if they recognize problematic patterns among an estimate's underlying assumptions. Rich problem representations aid pattern recognition, but auditors likely have difficulty developing them given auditors' limited domain-specific expertise in this area. In two experiments, I predict and find that a relational cue in a specialist's work highlighting aggressive assumptions improves auditors' problem representations and subsequent judgments about estimates. However, this improvement only occurs when a situational factor (e.g., risk) increases auditors' epistemic motivation to incorporate the cue into their problem representations. These results suggest that auditors do not always respond to cues in specialists' work. More generally, this study highlights the role of situational factors in increasing auditors' epistemic motivation to develop rich problem representations, which contribute to high-quality audit judgments in this and other domains where pattern recognition is important.

Role of Lys-226 in the Catalytic Mechanism ofBacillus StearothermophilusSerine HydroxymethyltransferaseCrystal Structure and Kinetic Studies†,‡

Biochemistry ◽  
2005 ◽  
Vol 44 (18) ◽  
pp. 6929-6937 ◽  
Author(s):  
Siddegowda Bhavani ◽  
V. Trivedi ◽  
V. R. Jala ◽  
H. S. Subramanya ◽  
Purnima Kaul ◽  
...  
Keyword(s):  
Catalytic Mechanism ◽  
Kinetic Studies

scholarly journals Using Regulatory Flexibility to Address Market Informality in Seed Systems: A Global Study

Agronomy ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 377
Author(s):  
Katrin Kuhlmann ◽  
Bhramar Dey
Keyword(s):  
Seed Quality ◽  
Regulatory Environment ◽  
Control Mechanisms ◽  
Seed Systems ◽  
High Quality ◽  
Design And Implementation ◽  
Key Dimensions ◽  
Regulatory Flexibility

Seed rules and regulations determine who can produce and sell seeds, which varieties will be available in the market, the quality of seed for sale, and where seed can be bought and sold. The legal and regulatory environment for seed impacts all stakeholders, including those in the informal sector, through shaping who can participate in the market and the quality and diversity of seed available. This paper addresses a gap in the current literature regarding the role of law and regulation in linking the informal and formal seed sectors and creating more inclusive and better governed seed systems. Drawing upon insights from the literature, global case studies, key expert consultations, and a methodology on the design and implementation of law and regulation, we present a framework that evaluates how regulatory flexibility can be built into seed systems to address farmers’ needs and engage stakeholders of all sizes. Our study focuses on two key dimensions: extending market frontiers and liberalizing seed quality control mechanisms. We find that flexible regulatory approaches and practices play a central role in building bridges between formal and informal seed systems, guaranteeing quality seed in the market, and encouraging market entry for high-quality traditional and farmer-preferred varieties.

scholarly journals Cavitation Bubble Cloud Break-Off Mechanisms at Micro-Channels

Fluids ◽  
2021 ◽  
Vol 6 (6) ◽  
pp. 215
Author(s):  
Paul McGinn ◽  
Daniel Pearce ◽  
Yannis Hardalupas ◽  
Alex Taylor ◽  
Konstantina Vogiatzaki
Keyword(s):  
Cavitation Bubble ◽  
Cavitation Inception ◽  
Wave Dynamics ◽  
Bubble Cloud ◽  
Cloud Dynamics ◽  
Micro Channels ◽  
Physical Insight ◽  
Cloud Process ◽  
Good Agreement

This paper provides new physical insight into the coupling between flow dynamics and cavitation bubble cloud behaviour at conditions relevant to both cavitation inception and the more complex phenomenon of flow “choking” using a multiphase compressible framework. Understanding the cavitation bubble cloud process and the parameters that determine its break-off frequency is important for control of phenomena such as structure vibration and erosion. Initially, the role of the pressure waves in the flow development is investigated. We highlight the differences between “physical” and “artificial” numerical waves by comparing cases with different boundary and differencing schemes. We analyse in detail the prediction of the coupling of flow and cavitation dynamics in a micro-channel 20 m high containing Diesel at pressure differences 7 MPa and 8.5 MPa, corresponding to cavitation inception and "choking" conditions respectively. The results have a very good agreement with experimental data and demonstrate that pressure wave dynamics, rather than the “re-entrant jet dynamics” suggested by previous studies, determine the characteristics of the bubble cloud dynamics under “choking” conditions.

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