Thesis advisor: Jeffery A. Byers / Chapter 1. Overview of Carbon Dioxide Hydrogenation for the Production of Formic Acid As the world’s energy demands increase, our resources dwindle and the need for a sustainable energy source is pertinent. Our current energy infrastructure is dominated by fossil fuel use. Hydrogen, on the other hand, is potentially an ideal energy carrier as it is emissions-free when burned and can be used in fuel cells. Significant advances are still needed to develop more efficient ways to produce and store H2. The hydrogenation of CO2 to formic acid and/or methanol provides an encouraging and reversible approach for a hydrogen storage material. The first example of homogeneously catalyzed hydrogenation of carbon dioxide was in 1976. Over the past 40 years, there has been excellent progress in the development of catalysts for CO2 hydrogenation. Typically, homogenous catalysts found to be effect are 2nd and 3rd row transition metals of groups 8-10. In recent years, base-metals (common and inexpensive metals) have demonstrated promising results. This chapter is designed to highlight important discoveries throughout the history of carbon dioxide hydrogenation. Chapter 2. Development of a Transition Metal / N-Heterocyclic Carbene Cooperative System for the Hydrogenation of Carbon Dioxide to Formic Acid Over the past few decades, the conversion of small molecules such as H2, N2, O2, CH4, C2H4, CO, and CO2 have attracted considerable attention. Many of these molecules are thermodynamically or kinetically stable and their usefulness depends on overcoming significant barriers. Frustrated Lewis pairs and N-heterocyclic carbenes have become common strategies to activate unreactive small molecule likes CO2 and H2. However, a hybrid approach utilizing both a transition metal and an activator has only recently been investigated for the transformation of small molecules to more useful and complex compounds. A novel method for these transformations is the use of a bifunctional catalyst system that incorporates a Lewis basic N-heterocyclic carbene and a Lewis acidic transition metal. This chapter highlights our serendipitous discovery that small quantities of bicarbonate and other inorganic salts enhanced the productivity of formic acid in CO2 hydrogenation reactions. The phenomenon was general for many noble-metal catalysts and for one of the most efficient base-metal hydrogenation catalysts. Additionally, the synthesis of a transition metal complex bearing a pendant dihydroimidazolium salt is described. Stoichiometric and catalytic applications of the newly designed complex were explored in investigate our Lewis base / transition metal approach to small molecule activation. Chapter 3. Chemistry of Iron N-Heterocyclic Carbene Complexes N-heterocyclic carbenes are one of the most versatile ligands in organometallic chemistry due to their unique properties as ancillary ligands. Although NHCs are typically potent σ-donors (a) with minor contributions from π*-backdonation (b), they also have the ability to accept electron density from the metal center as two-electron (c) or one-electron (d) interactions. Since the first examples of metal–NHC complexes were reported in the 1960’s, numerous studies have been devoted to the synthesis of new NHCs, to their characterization, and to their use as ligands in transition metal complexes. The coordination chemistry of NHCs with late transition metals has been studied extensively. However, the chemistry of iron–NHC complexes has not been developed to the same extent as other late transition metals. This chapter highlights important discoveries throughout the history of iron–NHC complexes, while emphasizing the nature of the metal–carbene bond. Chapter 4. Reactivity of Bis(amidinato)-N-Heterocyclic Carbene Iron Complexes Over the past few decades, the development of highly active and selective transition metal catalysts has attracted considerable attention. While the metal employed largely influences the expectations for catalytic activity, the importance of supporting ligands in tuning the reactivity of any given complex is vital. Our group recently synthesized a bis(amidinato)-N-heterocyclic carbene complex of iron as an analogy to the highly active bis(imino)pyridine iron complexes. We hypothesized that having an N-heterocyclic carbene as the central donor instead of pyridine could have significant impacts on the reactivity of such iron complexes. This chapter highlights the synthesis of iron bis(amidinato)-N-heterocyclic carbene complexes spanning multiple oxidation states previously described by our group. Through a combination characterization techniques, the bis(amidinato)-N-heterocyclic carbene was discovered to have unique interactions with the iron center, which change depending on the oxidation state of the metal. Additionally, we undertook investigations into the reactivity of these complexes with azides, hydrides, alkyl reagents, and ethylene. The results of which supported the capability of the bis(amidinato)-N-heterocyclic carbene ligand to act as a redox and chemical non-innocent ligand. / Thesis (MS) — Boston College, 2015. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Kian L. Tan / Utilization of directing groups in a general and efficient manner for highly regioselective hydroformylation of 1,1-disubstituted olefins. / Thesis (MS) — Boston College, 2011. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Amir H. Hoveyda / Chapter 1. Part A: N-Heterocyclic Carbenes Catalyzed Enantioselective Boryl Conjugate Additions to α,β-Unsaturated Ketones, Esters, Weinreb Amides and Aldehydes. The first broadly applicable enantioselective boryl conjugate addition reactions to a variety of α,β-unsaturated carbonyls are reported. Transformations are promoted by 5.0 mol % of a chiral Lewis basic N-heterocyclic carbene. The distinctive feature of the reactions in chemoselectivity of the method compared to the Cu-catalyzed variants has been illustrated. Part B: Enantioselective Synthesis of Boron-Substituted Quaternary Carbon Stereogenic Centers through N-Heterocyclic Carbenes Catalyzed Boryl Conjugate Additions to Cyclic and Acyclic Enones The first examples of Lewis base catalyzed enantioselective boryl conjugate additions that afford products containing boron-substituted quaternary carbon stereogenic centers are presented. The carbon–boron bond forming reactions are promoted by 1.0–5.0 mol % of a chiral N–hererocyclic carbene. Cyclic or linear α,β–unsaturated ketones can be used as suitable substrates and the desired products are obtained in 63–95% yield and 91:9 to >99:1 enantiomeric ratio. The utility of the Lewis base-catalyzed approach is demonstrated in the context of an enantioselective formal synthesis of antifungal natural product crassinervic acid. Chapter 2. Enantioselectivity Fluctuations in Phosphine–Cu-Catalyzed Enantioselective Boron-Allyl Addition to Aryl-Substituted Olefins. Catalytic enantioselective multicomponent processes involving B2(pin)2, aryl or heteroaryl monosubstituted olefins, and allylic phosphates or carbonates are disclosed. Transformations promoted by a chiral Cu–phosphine complex afford products that contain a primary C–B(pin) bond and an allyl-substituted tertiary carbon stereogenic center in up to 84% yield and 98:2 enantiomeric ratio. The utility of the approach is showcased in the enantioselective formal synthesis of biologically active heliespirones A and C. Based on mechanistic and computational studies, we show that enantioselectivities variations can depend on electronic and/or steric factors of the alkene substrate and the allyl electrophile as well as their concentration. In most cases, selectivity loss can be minimized and that the resulting insights are also applicable to reactions involving Cu–H species. Chapter 3. Synthesis of Vicinal Diboronate Compounds through Practical Phosphine–Copper Catalyzed Three-Component Processes. The phosphine–Cu-catalyzed multicomponent processes have been developed for a practical and direct synthesis of vicinal diboronate compounds. Reactions of alkenyl–boronates, allylic phosphates, and diboron reagents are promoted by 2.5–10 mol % of a Cy3P–Cu complex affording a wide range of desirable vicinal diboronate products. The ability for easy access to either regioisomers of the products with a C–B(pin) and an adjacent C–B(dan) bond that can be site-selectively functionalized is a noteworthy feature of the method. / Thesis (PhD) — Boston College, 2016. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

This thesis deals with the analytical study of vibration of carbon nanotubes and graphene plates. First, a brief overview of the traditional Bresse-Timoshenko models for thick beams and Uflyand-Mindlin models for thick plates will be conducted. It has been shown in the literature that the conventionally utilized mechanical models overcorrect the shear effect and that of rotary inertia. To improve the situation, two alternative versions of theories of beams and plates are proposed. The first one is derived through the use of equilibrium equations and leads to a truncated governing differential equation in displacement. It is shown, by considering a power series expansion of the displacement, that this is asymptotically consistent at the second order. The second theory is based on slope inertia and results in the truncated equation with an additional sixth order derivative term. Then, these theories will be extended in order to take into account some scale effects such as interatomic interactions that cannot be neglected for nanomaterials. Thus, different approaches will be considered: phenomenological, asymptotic and continualized. The basic principle of continualized models is to build continuous equations starting from discrete equations and by using Taylor series expansions or Padé approximants. For each of the different models derived in this study, the natural frequencies will be determined, analytically when the closed-form solution is available, numerically when the solution is given through a characteristic equation. The objective of this work is to compare the models and to establish the eventual superiority of a model on others. / Includes bibliography. / Dissertation (Ph.D.)--Florida Atlantic University, 2018. / FAU Electronic Theses and Dissertations Collection

by KE Ning. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves 127-134). / ACKNOWLEDGMENT --- p.a1 / ABSTRACT --- p.a2 / CONTENTS --- p.a3 / LIST OF FIGURE --- p.a6 / LIST OF TABLE --- p.a10 / Chapter CHAPTER 1 --- Introduction / Chapter 1.1 --- Overview of Some Carbon-Based Materials --- p.1 / Chapter 1.2 --- Diamond-Like Carbon (DLC) Thin Films --- p.3 / Chapter 1.2.1 --- Introduction --- p.3 / Chapter 1.2.2 --- Applications of DLC films --- p.9 / Chapter 1.2.3 --- The role of hydrogen --- p.10 / Chapter 1.2.4 --- The role of fluorine and the scope of this work --- p.13 / Chapter 1.3 --- Fullerenes --- p.17 / Chapter 1.3.1 --- Introduction --- p.17 / Chapter 1.3.2 --- Applications --- p.20 / Chapter 1.3.3 --- "The oxygen effect, the metal doping effect and the Scope of this study" --- p.23 / Chapter 1.4 --- Organization of This Thesis --- p.26 / Chapter CHAPTER 2 --- Experimental --- p.27 / Chapter 2.1 --- Samples Preparation and Thin Films Deposition --- p.27 / Chapter 2.1.1 --- Hydrogenated amorphous carbon thin film --- p.27 / Chapter 2.1.2 --- The fullerenes and C60 synthesis --- p.30 / Chapter 2.1.3 --- C60 thin film deposition --- p.34 / Chapter 2.2 --- Modification --- p.35 / Chapter 2.2.1 --- Ion implantation of a-C:H films --- p.35 / Chapter 2.2.2. --- C60doping --- p.39 / Chapter 2.3 --- Characterization Methods --- p.41 / Chapter 2.3.1 --- Electrical measurement --- p.41 / Chapter 2.3.2 --- High electric field measurement --- p.42 / Chapter 2.3.3 --- Electron Spin Resonance (ESR) --- p.43 / Chapter 2.3.4 --- Photoluminescence (PL) --- p.47 / Chapter 2.3.5 --- Photothermal Deflection Spectroscopy (PDS) --- p.48 / Chapter 2.3.6 --- Fourier Transform Infrared Spectrometry (FTIR) --- p.53 / Chapter 2.3.7 --- Mass Spectrum --- p.53 / Chapter CHAPTER 3 --- Characterization of the Fluorine implanted a-C:H Thin Films --- p.54 / Chapter 3.1 --- ESR Results --- p.55 / Chapter 3.2 --- Secondary Ion Mass Spectroscopy (SIMS) Measurement --- p.59 / Chapter 3.3 --- Electrical Properties --- p.61 / Chapter 3.4 --- Optical Properties --- p.65 / Chapter 3.4.1 --- PL Spectrum studies of fluorine implanted a-C:H films --- p.65 / Chapter 3.4.2 --- PDS Studies of fluorine implanted a-C:H films --- p.69 / Chapter 3.5 --- Nonlinear Transport Properties at High Fields --- p.76 / Chapter CHAPTER 4 --- Characterization of C60 Thin Films --- p.89 / Chapter 4.1 --- Effect of Oxygen on C60 Materials-The Stability Studies of C60 Films --- p.89 / Chapter 4.1.1 --- Defect studies-ESR measurements --- p.90 / Chapter 4.1.2 --- Structure studies of FTIR and Mass Spectrum measurements --- p.97 / Chapter 4.2 --- A Study of The Properties of Sn Doped C60 Films --- p.106 / Chapter 4.2.1 --- Surface Morphology --- p.107 / Chapter 4.2.2 --- The electrical and defect properties --- p.107 / Chapter 4.2.3 --- Optical study --- p.116 / Chapter 4.2.4 --- Structure analysis´ؤmass spectrum --- p.118 / Chapter CHAPTER 5 --- Conclusion --- p.121 / Chapter 5.1 --- Hydrogenated Amorphous Carbon --- p.121 / Chapter 5.2 --- Fullerene- C60 --- p.123 / Chapter CHAPTER 6 --- Future Works / Chapter 6.1 --- Amorphous Carbon Films --- p.125 / Chapter 6.2 --- C60 Materials --- p.125 / REFERENCES --- p.127 / APPENDIX / Chapter 1 --- ESR Results of Fluorine Implanted a-C:H Films --- p.i / Chapter 2 --- Publications --- p.ii

Multiwall carbon nanotubes filled with continuous single-crystals of the ferromagnetic phase -Fe were produced with two new synthesis methods: the boundary layer chemical vapour synthesis and the perturbed vapour chemical vapour deposition. In the first method, the nanotubes nucleate and grow radially from a central agglomeration of homogeneously nucleated spherical particles in a randomly fluctuating vapour created in the viscous boundary layer between a rough surface and a laminar pyrolyzed-ferrocene/Ar vapour flow. In the second method, the nanotubes nucleate and form in a flower-like arrangement departing from homogeneously nucleated particles. These particles are produced by the creation of a local perturbation in a vapour with a high density of Fe and C species obtained from the pyrolysis of ferrocene in a laminar Ar flow. Electron microscopy investigations revealed that the continuous single crystals obtained with both methods exhibit diameters much lower than the critical diameter for a single magnetic domain of -Fe (~ 66 nm). In the radial structures, the single-crystal diameter is in the range of ~ 17-37 nm, while in the flower-like structures the single crystals show mainly a diameter of ~ 30 nm and ~ 55 nm. The average single crystals length is 7-8 m in the case of the radial structures and 19-21 m in the case of the flower-like structures. DC magnetization measurements at 5 K show different magnetic behaviours. The flower-like structures present a very high saturation magnetization of 189.5 emu/g and a high coercivity of 580 Oe. The radial structures exhibit an exchange-coupled ferromagnetic/antiferromagnetic system despite only 2% of -Fe is present inside the nanotubes. The radial structures obtained at flow-rates of 3.5 ccm and 20 ccm, show saturation-magnetizations of 31emu/g and 13 emu/g, and coercivities of 790 Oe and 843 Oe respectively.

本論文的研究包括Co(por)Ar的合成和對Ar-I鍵被Co(por)活化的机理研究。首先，一系列Co(por)Ar成功的由Co(por)和取代碘帶苯在150 ℃和氫氧化鉀的作用下合成并得到中等到高的产率。 / 其次，自由能研究表明 Co(por)對Ar-I键的活化是通过碘原子轉移進行的。相对速率k[subscript rel]从取代碘代苯和碘代苯同Co(por)的競爭反應得出。自由能關係研究表明logk[subscript rel]同取代常數σp-的哈密特相关给出一斜率為1.02的直線，表明高度離域的负电荷在苯环的增加和碘原子的π電子同對位取代基在過渡態的共軛。基于这个事实和对其它机理的排除得出Co(por)對Ar-I键的活化的機理為碘原子轉移機理。因此， Co[superscript II](ttp)首先同ArI反應形成一個直線型過渡態[Co(ttp)---I---Ar]，而後生成Co(ttp)I同一個苯自由基(Ar·)。Ar同Co[superscript II](ttp)反應生成Co(ttp)Ar，Co(ttp)I同 KOH反應生成Co[superscript II](ttp)和H₂O₂，並且Co[superscript II](ttp)同ArI繼續反應。 / This research includes the synthesis of cobalt porphyrin aryl complexes (Co(por)Ar) and mechanistic study of the aryl-iodine (Ar-I) bond activation by Co(por). First, a series of cobalt porphyrin aryl complexes, Co(por)Ar, were successfully synthesized from Co(por) and aryl iodides in moderate to high yield in the presence of potassium hydroxide at 150°C. / Second, the free energy relationship study demonstrates that Ar-I bonds are activated by cobalt porphyrin (Co(por)) through an iodine atom transfer pathway. The relative rates (k[subscript rel]) were derived from competition reactions of substituted aryl iodides and phenyl iodide with Co(por). The free energy relationship study illustrates that the krel against σp - yields linear behavior with positive slope (ρ = 1.02), suggesting that a highly delocalized negative charge builds on the aryl ring, and conjugation of π-electron density of iodine atom with para substituents occurs in the transition state. With this fact and the exclusion of other possible mechanisms, it is concluded that the mechanism of activation of Ar-I bond by Co(por) involves iodine atom transfer pathway. Thus, Co[superscript II](ttp) reacts with ArI to form a linear transition state [Co(ttp)---I---Ar], which then yields Co(ttp)I and an aryl radical (Ar·). Ar· reacts with Co(ttp) to give Co(ttp)Ar, Co(ttp)I reacts with KOH to give Co[superscript II](ttp) and H₂O₂, and Co(ttp) continues to react with ArI. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Li, Chen. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 50-55). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts also in Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iv / Abbreviations --- p.v / Abstract --- p.vi / Structural Abbreviations for Porphyrins --- p.ix / Chapter Chapter 1 --- General Introduction --- p.1 / Chapter 1.1 --- Application of Cobalt Porphyrin Complexes --- p.1 / Chapter 1.2 --- Energy Level Diagram for Cobalt Porphyrin Complexes --- p.1 / Chapter 1.3 --- Co(I) Porphyrin Chemistry --- p.2 / Chapter 1.4 --- Co(II) Porphyrin Chemistry --- p.3 / Chapter 1.5 --- Co(III) Porphyrin Chemistry --- p.5 / Chapter 1.6 --- Activation of Aryl Carbon-Halogen bond by Cobalt Complexes --- p.5 / Chapter 1.6.1 --- Definination of pathways of activation of aryl carbon-halogen bond by transition metals --- p.5 / Chapter 1.6.2 --- Bond dissociation energy (BDE) of Aryl halides --- p.6 / Chapter 1.6.3 --- Mechanism of aryl carbon-halogen bond activation by cobalt complex --- p.7 / Chapter 1.6.3.1 --- Oxidative addition --- p.7 / Chapter 1.6.3.2 --- Nucleophilic Aromatic Substitution --- p.8 / Chapter 1.6.3.3 --- Radical pathway --- p.9 / Chapter 1.7 --- Free energy relationship study of aryl-halide bond activation by transition metal complexes --- p.13 / Chapter 1.7.1 --- Oxidative addition of aryl-halide bond by transition metal complexes --- p.13 / Chapter 1.7.2 --- Aryl-halide bond acitvation by transition metal complexes via radical pathway --- p.18 / Chapter 1.8 --- Objectives of the work --- p.21 / Chapter Chapter 2 --- Mechanistic study of Bond Activation of Aryl Carbon-Iodide (C-I) Bonds by Cobalt(II) Porphyrin --- p.22 / Chapter 2.1 --- Background --- p.22 / Chapter 2.2 --- Aryl Carbon-iodide (C-I) bond Activation by Co(II) Porphyrins --- p.22 / Chapter 2.3 --- Preparation of Starting Materials --- p.23 / Chapter 2.3.1 --- Synthesis of Porphyrins --- p.23 / Chapter 2.3.2 --- Synthesis of Cobalt(II) Porphyrins --- p.23 / Chapter 2.4 --- Optimization of the reaction conditions --- p.24 / Chapter 2.4.1 --- Optimization of Substrate, Base and Additive --- p.24 / Chapter 2.4.2 --- Temperature Optimization --- p.24 / Chapter 2.5 --- Halogen Atoms Effect on the Cleavage Rates of Ph-X (X = Br, Cl) Bonds --- p.25 / Chapter 2.6 --- Substrate Scope of Base-Promoted Aryl C-I Activation by Co[superscript II](ttp) --- p.26 / Chapter 2.7 --- Porphyrin Scope --- p.27 / Chapter 2.8 --- X-Ray Data of Cobalt(III) Porphyrin Aryls --- p.28 / Chapter 2.9 --- Mechanistic Study of Aryl C-I Bond Activation by Co[superscript II](ttp) --- p.29 / Chapter 2.9.1 --- Possible Mechanistic Pathway --- p.29 / Chapter 2.9.2 --- Competition Reactions --- p.30 / Chapter 2.9.3 --- Free energy relationship study --- p.32 / Chapter 2.9.4 --- Mechanism discussion --- p.33 / Chapter 2.9.4.1 --- Nucleophilic Aromatic Substitution --- p.33 / Chapter 2.9.4.2 --- Oxiative Addition --- p.33 / Chapter 2.9.4.3 --- Radical ipso-Substitution --- p.34 / Chapter 2.9.4.4 --- Electron Transfer and Iodine Atom Transfer pathways --- p.34 / Chapter 2.10 --- Conclusions --- p.37 / Chapter Chapter 3 --- Experimental Section --- p.38 / References --- p.50 / Appendix --- p.56

"Carbon is one of the most abundant non-metal elements in the world. The unique arrangement of electrons enables diverse properties and applications of carbon. Long before the discovery of C60 in 1985, which is now considered a milestone in the vibrant field of carbon nanotechnology, carbon has been a vital part of human history. It has been a key enabling material in many fields including aerospace, transportation, energy storage, electric devices, infrared sensors, etc. The report of fullerene triggered a feverish surge of interest and effort in the study of nanostructured carbon. Along with the discovery of carbon nanotubes (CNTs) and graphene nanosheets (GNS), the nanocarbon family has been extensively studied. However, controlled production of carbon nanomaterials with low cost and high efficiency and incorporation of nanocarbons to maximize their contribution in advanced applications still faces a lot of technical difficulties. The objective of this work is to study and optimize processes to synthesize multiwall carbon nanotubes (MWCNTs) and GNS, and to apply GNS in nanocomposite anode materials for Lithium ion batteries (LIBs). Therefore, in this thesis, there are three main parts: (1) development of the post-processing method to obtain free-standing CNT arrays by the template-assisted chemical vapor deposition (CVD) method; (2) development of a synthesis protocol to obtain GNS by oxidation of natural graphite flakes and reduction of the resulted graphene oxides; and (3) fabrication of TiO2/GNS in core-shell structure by a static electric assembling method to improve anode performance for LIB applications."

"The increasing global demands for materials and energy directly contributes to the devastating ecological, toxicological, and climate consequences currently observed. Biomass-derived energy and materials offers a sustainable option to meeting current needs and developing novel materials. Hydrothermal carbonization is a promising green platform to valorize biomass by forming Hydrochar, a carbon solid. Hydrothermal carbonization converts biomass using liquid phase water at elevated temperatures (180-350 °C), forming organic intermediates, which dehydrate and polymerize to form the solid material on time scales of several hours. Hydrochar shows promise for a wide variety of applications, including aqueous heavy-metal adsorption. The complexity of the hydrochar prevents reliable characterization, hindering a full understanding of how to optimize the material. The focus of this study was to develop spectroscopic methods better understand the material as it changes with reaction time (ex-situ). This study developed IR and Raman Spectroscopy and Mass Spectrometry (MS) methods. Hydrochars were prepared from glucose (a model for biomass) and were prepared at different reaction times between 3 and 24 hours to understand the formation of the material and how it matures under process conditions (180 °C, autogenous pressure). IR and MS identified hydroxyl and ketone functionalities and aliphatic, furanic, and aromatic moieties, and both techniques indicated decreasing hydroxyl and furan content and increasing methyl and aromatic content. The Raman spectra were consistent with aldehyde-functionalized 1- and 2-ring arenes and aldehyde-functionalized furans, and indicated increasing 2-ring arene content relative to 1-ring arenes. MS showed a significant increase in the aromatic to furan ratio, and MS confirmed the increase in 2-ring arenes relative to 1-ring arenes seen in the Raman. These spectroscopic methods are in good agreement and will allow for greater chemical information in the hydrochar, which will inform the link between material modification under process conditions and application performance."

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