940 resultados para Niobium carbide
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In this work the growth and the magnetic properties of the transition metals molybdenum, niobium, and iron and of the highly-magnetostrictive C15 Laves phases of the RFe2 compounds (R: Rare earth metals: here Tb, Dy, and Tb{0.3}Dy{0.7} deposited on alpha-Al2O3 (sapphire) substrates are analyzed. Next to (11-20) (a-plane) oriented sapphire substrates mainly (10-10) (m-plane) oriented substrates were used. These show a pronounced facetting after high temperature annealing in air. Atomic force microscopy (AFM) measurements reveal a dependence of the height, width, and angle of the facets with the annealing temperature. The observed deviations of the facet angles with respect to the theoretical values of the sapphire (10-1-2) and (10-11) surfaces are explained by cross section high resolution transmission electron microscopy (HR-TEM) measurements. These show the plain formation of the (10-11) surface while the second, energy reduced (10-1-2) facet has a curved shape given by atomic steps of (10-1-2) layers and is formed completely solely at the facet ridges and valleys. Thin films of Mo and Nb, respectively, deposited by means of molecular beam epitaxy (MBE) reveal a non-twinned, (211)-oriented epitaxial growth as well on non-faceted as on faceted sapphire m-plane, as was shown by X-Ray and TEM evaluations. In the case of faceted sapphire the two bcc crystals overgrow the facets homogeneously. Here, the bcc (111) surface is nearly parallel to the sapphire (10-11) facet and the Mo/Nb (100) surface is nearly parallel to the sapphire (10-1-2) surface. (211)-oriented Nb templates on sapphire m-plane can be used for the non-twinned, (211)-oriented growth of RFe2 films by means of MBE. Again, the quality of the RFe2 films grown on faceted sapphire is almost equal to films on the non-faceted substrate. For comparison thin RFe2 films of the established (110) and (111) orientation were prepared. Magnetic and magnetoelastic measurements performed in a self designed setup reveal a high quality of the samples. No difference between samples with undulated and flat morphology can be observed. In addition to the preparation of covering, undulating thin films on faceted sapphire m-plane nanoscopic structures of Nb and Fe were prepared by shallow incidence MBE. The formation of the nanostructures can be explained by a shadowing of the atomic beam due to the facets in addition to de-wetting effects of the metals on the heated sapphire surface. Accordingly, the nanostructures form at the facet ridges and overgrow them. The morphology of the structures can be varied by deposition conditions as was shown for Fe. The shape of the structures vary from pearl-necklet strung spherical nanodots with a diameter of a few 10 nm to oval nanodots of a few 100 nm length to continuous nanowires. Magnetization measurements reveal uniaxial magnetic anisotropy with the easy axis of magnetization parallel to the facet ridges. The shape of the hysteresis is depending on the morphology of the structures. The magnetization reversal processes of the spherical and oval nanodots were simulated by micromagnetic modelling and can be explained by the formation of magnetic vortices.
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Die Photoemissions-Elektronenmikroskopie ist eine hervorragend geeignete Methode zur Untersuchung dynamischer Vorgänge auf realen polykristallinen Oberflächen im sub-μm Bereich. Bei der Anwendung auf Adsorbatsysteme lassen sich geringe Bedeckungsunterschiede, sowie Adsorbatstrukturen und -phasen unterscheiden. Die Methode erlaubt dabei ein breites Anwendungsspektrum über weite Temperaturbereiche und Systeme unterschiedlichster Bindungsenergie. Bei der Chemisorption von Sauerstoff auf polykristallinen Metallen wird unterschiedliches Aufwachsverhalten in den Helligkeitswerten im Mikroskopbild widergespiegelt. Bei Kupferproben zeigen Oberflächen mit unterschiedlicher kristalliner Richtung aufgrund der Symmetrie des fcc-Gitters ein ähnliches Verhalten. Das hexagonale Gitter des Titans zeigt dagegen große Unterschiede im Adsorptionsverhalten in Abhängigkeit der kristallinen Richtung. Diese Unterschiede konnten auf verschiedene Haftkoeffizienten und Oxidationsstufen der Metalle zurückgeführt werden. In einem Modell zur Photostromanalyse konnte beim Kupfer der Übergang von verschiedenen Überstrukturen bei wachsender Bedeckung gezeigt und die Übergänge ermittelt werden.. Auf den Titanoberflächen wurde so das Wachstum der Oxide TiO, TiO2 und Ti2O3 unterschieden und die Übergänge des unterschiedlichen Wachstums ermittelt. Bei der thermischen Desorption der Schichten konnten unterschiedliche Haftkoeffizient auf einzelnen Kristalliten qualitativ gezeigt werden. Diese erstmalig eingesetzte Analysemethode weist Ähnlichkeiten zur Thermo-Desorptions-Spektroskopie (TDS) auf, zeigt jedoch ortsaufgelöst lokale Unterschiede auf polykristallinen Oberflächen. Bei thermisch gestützten Oberflächenreaktionen ließen sich die Reaktionskeime deutlich identifizieren und mit einer Grauwertanalyse konnte die Oxidation der karbidischen Lagen zu Kohlenmonoxid und die Metalloxidation unterschieden werden. Dabei konnte gezeigt werden, daß die Reaktionskeime nur an Plattengrenzen auftreten, nicht jedoch auf der Oberfläche. Durch die Aufrauhung der Plattengrenzen mit zunehmender Reaktionsdauer nimmt die Zahl der Reaktionskeime kontinuierlich zu, die laterale Ausdehnung der Einzelreaktionen bleibt aber konstant. Bei der Physisorption von Xenon auf Graphit wurde erstmals für die Photoemissionsmikroskopie die resonanten Anregung ausgenutzt. Die verschiedenen Phasen des Adsorbats können dabei deutlich unterschieden werden; bei niedrigen Temperaturen (40K) findet ein gleichmäßiges Wachstum auf der gesamten Oberfläche statt, bei höheren Temperaturen von 60-65K ist dagegen ein Inselwachstum in verschiedenen Phasen zu beobachten. Die zeitliche Entwicklung des Wachstums, die örtliche Lage der Phasen und die Phasenübergänge (gas, fest inkommensurabel, fest kommensurabel) konnten bestimmt werden. Bei der Desorption der Schichten konnten die einzelnen Phasen ebenfalls getrennt werden und das unterschiedliche Desorptionsverhalten sowie die Phasenübergänge selber verifiziert werden.
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Durante l'attività di ricerca sono stati sviluppati tre progetti legati allo sviluppo e ottimizzazione di materiali compositi. In particolare, il primo anno, siamo andati a produrre materiali ceramici ultrarefrattari tenacizzati con fibre di carburo di silicio, riuscendo a migliorare il ciclo produttivo e ottenendo un materiale ottimizzato. Durante il secondo anno di attività ci siamo concentrati nello sviluppo di resine epossidiche rinforzate con particelle di elastomeri florurati che rappresentano un nuovo materiale non presente nel mercato utile per applicazioni meccaniche e navali. L'ultimo anno di ricerca è stato svolto presso il laboratorio materiali di Ansaldo Energia dove è stato studiato il comportamenteo di materiali per turbine a gas.
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The present thesis is focused on the study of innovative Si-based materials for third generation photovoltaics. In particular, silicon oxi-nitride (SiOxNy) thin films and multilayer of Silicon Rich Carbide (SRC)/Si have been characterized in view of their application in photovoltaics. SiOxNy is a promising material for applications in thin-film solar cells as well as for wafer based silicon solar cells, like silicon heterojunction solar cells. However, many issues relevant to the material properties have not been studied yet, such as the role of the deposition condition and precursor gas concentrations on the optical and electronic properties of the films, the composition and structure of the nanocrystals. The results presented in the thesis aim to clarify the effects of annealing and oxygen incorporation within nc-SiOxNy films on its properties in view of the photovoltaic applications. Silicon nano-crystals (Si NCs) embedded in a dielectric matrix were proposed as absorbers in all-Si multi-junction solar cells due to the quantum confinement capability of Si NCs, that allows a better match to the solar spectrum thanks to the size induced tunability of the band gap. Despite the efficient solar radiation absorption capability of this structure, its charge collection and transport properties has still to be fully demonstrated. The results presented in the thesis aim to the understanding of the transport mechanisms at macroscopic and microscopic scale. Experimental results on SiOxNy thin films and SRC/Si multilayers have been obtained at macroscopical and microscopical level using different characterizations techniques, such as Atomic Force Microscopy, Reflection and Transmission measurements, High Resolution Transmission Electron Microscopy, Energy-Dispersive X-ray spectroscopy and Fourier Transform Infrared Spectroscopy. The deep knowledge and improved understanding of the basic physical properties of these quite complex, multi-phase and multi-component systems, made by nanocrystals and amorphous phases, will contribute to improve the efficiency of Si based solar cells.
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The project of this Ph.D. thesis is based on a co-supervised collaboration between Università di Bologna, ALMA MATER STUDIORUM (Italy) and Instituto de Tecnología Química, Universitat Politècnica de València ITQ-UPV (Spain). This Ph.D. thesis is about the synthesis, characterization and catalytic testing of complex mixed-oxide catalysts mainly related to the family of Hexagonal Tungsten Bronzes (HTBs). These materials have been little explored as catalysts, although they have a great potential as multifunctional materials. Their peculiar acid properties can be coupled to other functionalities (e.g. redox sites) by isomorphous substitution of tungsten atoms with other transition metals such as vanadium, niobium and molybdenum. In this PhD thesis, it was demonstrated how it is possible to prepare substituted-HTBs by hydrothermal synthesis; these mixed-oxide were fully characterize by a number of physicochemical techniques such as XPS, HR-TEM, XAS etc. They were also used as catalysts for the one-pot glycerol oxidehydration to acrylic acid; this reaction might represent a viable chemical route to solve the important issue related to the co-production of glycerin along the biodiesel production chain. Acrylic acid yields as high as 51% were obtained and important structure-reactivity correlations were proved to govern the catalytic performance; only fine tuning of acid and redox properties as well as the in-framework presence of vanadium are fundamental to achieve noteworthy yields into the acid monomer. The overall results reported herein might represent an important contribution for future applications of HTBs in catalysis as well as a general guideline for a multifaceted approach for their physicochemical characterization.
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Negli ultimi anni si è assistito ad un notevole sviluppo e diffusione dei sistemi di produzione di energia rinnovabile, in particolar modo di sistemi eolici e fotovoltaici. La sempre maggior richiesta di energia e la necessità di far fronte ai problemi di inquinamento sempre più intenso, a causa dei combustibili fossili, ha portato ad una crescita nell’interesse ad adottare queste nuove tecnologie per il sostentamento energetico della popolazione. In seguito all’adozione di tali sistemi si è verificata un’intensificazione della ricerca e dello sviluppo tecnologico in tale ambito al fine di massimizzare la produzione dell’energia. Un ruolo chiave nella gestione dell’energia ed in particolar modo l’interfacciamento del sistema di produzione con il carico è svolto elettronica di potenza. L’obiettivo principale della ricerca in tale ambito consiste nella individuazione di nuove tecnologie che permettano un incremento dell’efficienza di conversione anche di soli pochi punti percentuale. L’attività di tesi, svolta presso il LEMAD (Laboratorio di Macchine e Azionamenti del Dipartimento DEI), è stata quindi focalizzata nella progettazione e in seguito realizzazione di un convertitore per applicazioni fotovoltaiche. L’interesse nei confronti delle nuovetecnologie ha portato ad una scelta innovativa per quanto riguarda la configurazione dell’inverter costituente il convertitore. Tale configurazione, che prende il nome di Full Bridge DC Bypass o più semplicemente ponte H6, ha permesso la realizzazione di un convertitore compatto poiché non necessitante di un trasformatore per garantire l’isolamento tra i moduli PV e la rete. Inoltre l’adozione di due switch aggiuntivi rispetto ad un comune ponte H ha garantito una notevole riduzione delle perdite dovute alla tensione di modo comune(CMV)con conseguente incremento dell’efficienza. La ricerca di nuove tecnologie non è stata concentrata solamente nello studio di nuove configurazioni di inverter ma anche nell’individuazione di innovativi dispositivi di potenza. In particolar modo il silicon carbide o SiC ha dimostrato in diverse occasioni di essere un materiale superiore al silicio nelle applicazioni di potenza. Sono stati quindi realizzati due convertitori utilizzanti due differenti dispositivi di potenza (MOSFET in SiC e IGBT in Si)in modo tale da determinare le diverse prestazioni. Un ulteriore studio è stato svolto sulle tecniche di modulazione al fine di valutarne le differenti caratteristiche ed individuare quella più conveniente nella conversione utilizzante il ponte H6.
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AIM: To describe a method of carrying out apical surgery of a maxillary molar using ultrasonics to create a lateral sinus window into the maxillary sinus and an endoscope to enhance visibility during surgery. SUMMARY: A 37-year-old female patient presented with tenderness to percussion of the maxillary second right molar. Root canal treatment had been undertaken, and the tooth restored with a metal-ceramic crown. Radiological examination revealed an apical radiolucency in close proximity to the maxillary sinus. Apical surgery of the molar was performed through the maxillary sinus, using ultrasonics for the osteotomy, creating a window in the lateral wall of the maxillary sinus. During surgery, the lining of the sinus was exposed and elevated without perforation. The root-end was resected using a round tungsten carbide drill, and the root-end cavity was prepared with ultrasonic retrotips. Root-end filling was accomplished with MTA(®) . An endoscope was used to examine the cut root face, the prepared cavity and the root-end filling. No intraoperative or postoperative complications were observed. At the 12-month follow-up, the tooth had no clinical signs or symptoms, and the radiograph demonstrated progressing resolution of the radiolucency. KEY LEARNING POINTS: When conventional root canal retreatment cannot be performed or has failed, apical surgery may be considered, even in maxillary molars with roots in close proximity to the maxillary sinus. Ultrasonic sinus window preparation allows more control and can minimize perforation of the sinus membrane when compared with conventional rotary drilling techniques. The endoscope enhances visibility during endodontic surgery, thus improving the quality of the case.
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This study evaluated the operator variability of different finishing and polishing techniques. After placing 120 composite restorations (Tetric EvoCeram) in plexiglassmolds, the surface of the specimens was roughened in a standardized manner. Twelve operators with different experience levels polished the specimens using the following finishing/polishing procedures: method 1 (40 ?m diamond [40D], 15 ?m diamond [15D], 42 ?m silicon carbide polisher [42S], 6 ?m silicon carbide polisher [6S] and Occlubrush [O]); method 2 (40D, 42S, 6S and O); method 3 (40D, 42S, 6S and PoGo); method 4 (40D, 42S and PoGo) and method 5 (40D, 42S and O). The mean surface roughness (Ra) was measured with a profilometer. Differences between the methods were analyzed with non-parametric ANOVA and pairwise Wilcoxon signed rank tests (?=0.05). All the restorations were qualitatively assessed using SEM. Methods 3 and 4 showed the best polishing results and method 5 demonstrated the poorest. Method 5 was also most dependent on the skills of the operator. Except for method 5, all of the tested procedures reached a clinically acceptable surface polish of Ra?0.2 ?m. Polishing procedures can be simplified without increasing variability between operators and without jeopardizing polishing results.
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SUMMARY The aim of this study was to evaluate the influence of surface roughness on surface hardness (Vickers; VHN), elastic modulus (EM), and flexural strength (FLS) of two computer-aided design/computer-aided manufacturing (CAD/CAM) ceramic materials. One hundred sixty-two samples of VITABLOCS Mark II (VMII) and 162 samples of IPS Empress CAD (IPS) were ground according to six standardized protocols producing decreasing surface roughnesses (n=27/group): grinding with 1) silicon carbide (SiC) paper #80, 2) SiC paper #120, 3) SiC paper #220, 4) SiC paper #320, 5) SiC paper #500, and 6) SiC paper #1000. Surface roughness (Ra/Rz) was measured with a surface roughness meter, VHN and EM with a hardness indentation device, and FLS with a three-point bending test. To test for a correlation between surface roughness (Ra/Rz) and VHN, EM, or FLS, Spearman rank correlation coefficients were calculated. The decrease in surface roughness led to an increase in VHN from (VMII/IPS; medians) 263.7/256.5 VHN to 646.8/601.5 VHN, an increase in EM from 45.4/41.0 GPa to 66.8/58.4 GPa, and an increase in FLS from 49.5/44.3 MPa to 73.0/97.2 MPa. For both ceramic materials, Spearman rank correlation coefficients showed a strong negative correlation between surface roughness (Ra/Rz) and VHN or EM and a moderate negative correlation between Ra/Rz and FLS. In conclusion, a decrease in surface roughness generally improved the mechanical properties of the CAD/CAM ceramic materials tested. However, FLS was less influenced by surface roughness than expected.
Enamel loss and adhesive remnants following bracket removal and various clean-up procedures in vitro
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This study evaluated the enamel loss and composite remnants after debonding and clean-up. The tested null hypothesis is that there are no differences between different polishing systems regarding removing composite remnants without damaging the tooth surface. Brackets were bonded to 75 extracted human molars and removed after a storage period of 100 hours. The adhesive remnant index (ARI) was evaluated. The clean-up was carried out with five different procedures: 1. carbide bur; 2. carbide bur and Brownie and Greenie silicone polishers; 3. carbide bur and Astropol polishers; 4. carbide bur and Renew polishers; and 5. carbide bur, Brownie, Greenie and PoGo polishers. Silicone impressions were made at baseline (T0) and after debonding (T1) and polishing (T2) to produce plaster replicas. The replicas were analysed with a three-dimensional laser scanner and measured with analytical software. Statistical analysis was performed with the Kruskal-Wallis test and pairwise Wilcoxon tests with Bonferroni-Holm adjustment (α = 0.05). Enamel breakouts after debonding were detectable in 27 per cent of all cases, with a mean volume loss of 0.02 mm(3) (±0.03 mm(3)) and depth of 44.9 μm (±48.3 μm). The overall ARI scores was 3 with a few scores of 1 and 2. The composite remnants after debonding had a mean volume of 2.48 mm(3) (±0.92 mm(3)). Mean volume loss due to polishing was 0.05 mm(3) (±0.26 mm(3)) and the composite remnants had a mean volume of 0.22 mm(3) (±0.32 mm(3)). There were no statistically significant differences in volumetric changes after polishing (P = 0.054) between the different clean-up methods. However, sufficient clean-up without enamel loss was difficult to achieve.
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The use of metal implants in dental and orthopedic surgery is continuously expanding and highly successful. While today longevity and load-bearing capacity of the implants fulfill the expectations of the patients, acceleration of osseointegration would be of particular benefit to shorten the period of convalescence. To further clarify the options to accelerate the kinetics of osseointegration, within this study, the osteogenic properties of structurally identical surfaces with different metal coatings were investigated. To assess the development and function of primary human osteoblasts on metal surfaces, cell viability, differentiation, and gene expression were determined. Titanium surfaces were used as positive, and surfaces coated with gold were used as negative controls. Little differences in the cellular parameters tested for were found when the cells were grown on titanium discs sputter coated with titanium, zirconium, niobium, tantalum, gold, and chromium. Cell number, activity of cell layer-associated alkaline phosphatase (ALP), and levels of transcripts encoding COL1A1 and BGLAP did not vary significantly in dependence of the surface chemistry. Treatment of the cell cultures with 1,25(OH)2 D3 /Dex, however, significantly increased ALP activity and BGLAP messenger RNA levels. The data demonstrate that the metal layer coated onto the titanium discs exerted little modulatory effects on cell behavior. It is suggested that the microenvironment regulated by the peri-implant tissues is more effective in regulating the tissue response than is the material of the implant itself.
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This in vitro study aimed to assess the speed and caries removal effectiveness of four different new and conventional dentine excavation methods. Eighty deciduous molars were assigned to four groups. Teeth were sectioned longitudinally through the lesion centre. Images of one half per tooth were captured by light microscope and confocal laser scanning microscopy (CLSM) to assess the caries extension. The halves were then reassembled and caries removed using round carbide bur (group 1), Er:YAG laser (group 2), hand excavator (group 3) and a polymer bur (group 4). The time needed for the whole excavation in each tooth was registered. After excavation, the halves were photographed by light microscope. Caries extension obtained from CLSM images were superimposed on the post-excavation images, allowing comparison between caries extension and removal. The regions where caries and preparation limits coincided, as well as the areas of over- and underpreparation, were measured. Steel bur was the fastest method, followed by the polymer bur, hand excavator and laser. Steel bur exhibited also the largest overpreparation area, followed by laser, hand excavator and polymer bur. The largest underpreparation area was found using polymer bur, followed by laser, hand excavator and steel bur. Hand excavator presented the longest coincidence line, followed by polymer and steel burs and laser. Overall, hand excavator seemed to be the most suitable method for carious dentine excavation in deciduous teeth, combining good excavation time with effective caries removal.
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Phosphomolybdic acid (H3PMo12O40) along with niobium,pyridine and niobium exchanged phosphomolybdic acid catalysts were prepared. Ammonia adsorption microcalorimetry and methanol oxidation studies were carried out to investigate the acid sites strength acid/base/redox properties of each catalyst. The addition of niobium, pyridine or both increased the ammonia heat of adsorption and the total uptake. The catalyst with both niobium and pyridine demonstrated the largest number of strong sites. For the parent H3PMo12O40 catalyst, methanol oxidation favors the redox product. Incorporation of niobium results in similar selectivity to redox products but also results in no catalyst deactivation. Incorporation of pyridine instead changes to the selectivity to favor the acidic product. Finally, the inclusion of both niobium and pyridine results in strong selectivity to the acidic product while also showing no catalyst deactivation. Thus the presence of pyridine appears to enhance the acid property of the catalyst while niobium appears to stabilize the active site.
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Attempts to strengthen a chromium-modified titanium trialuminide by a combination of grain size refinement and dispersoid strengthening led to a new means to synthesize such materials. This Reactive Mechanical Alloying/Milling process uses in situ reactions between the metallic powders and elements from a process control agent and/or a gaseous environment to assemble a dispersed small hard particle phase within the matrix by a bottom-up approach. In the current research milled powders of the trialuminide alloy along with titanium carbide were produced. The amount of the carbide can be varied widely with simple processing changes and in this case the milling process created trialuminide grain sizes and carbide particles that are the smallest known from such a process. Characterization of these materials required the development of x-ray diffraction means to determine particle sizes by deconvoluting and synthesizing components of the complex multiphase diffraction patterns and to carry out whole pattern analysis to analyze the diffuse scattering that developed from larger than usual highly defective grain boundary regions. These identified regions provide an important mass transport capability in the processing and not only facilitate the alloy development, but add to the understanding of the mechanical alloying process. Consolidation of the milled powder that consisted of small crystallites of the alloy and dispersed carbide particles two nanometers in size formed a unique, somewhat coarsened, microstructure producing an ultra-high strength solid material composed of the chromium-modified titanium trialuminide alloy matrix with small platelets of the complex carbides Ti2AlC and Ti3AlC2. This synthesis process provides the unique ability to nano-engineer a wide variety of composite materials, or special alloys, and has shown the ability to be extended to a wide variety of metallic materials.
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A novel solution to the long standing issue of chip entanglement and breakage in metal cutting is presented in this dissertation. Through this work, an attempt is made to achieve universal chip control in machining by using chip guidance and subsequent breakage by backward bending (tensile loading of the chip's rough top surface) to effectively control long continuous chips into small segments. One big limitation of using chip breaker geometries in disposable carbide inserts is that the application range is limited to a narrow band depending on cutting conditions. Even within a recommended operating range, chip breakers do not function effectively as designed due to the inherent variations of the cutting process. Moreover, for a particular process, matching the chip breaker geometry with the right cutting conditions to achieve effective chip control is a very iterative process. The existence of a large variety of proprietary chip breaker designs further exacerbates the problem of easily implementing a robust and comprehensive chip control technique. To address the need for a robust and universal chip control technique, a new method is proposed in this work. By using a single tool top form geometry coupled with a tooling system for inducing chip breaking by backward bending, the proposed method achieves comprehensive chip control over a wide range of cutting conditions. A geometry based model is developed to predict a variable edge inclination angle that guides the chip flow to a predetermined target location. Chip kinematics for the new tool geometry is examined via photographic evidence from experimental cutting trials. Both qualitative and quantitative methods are used to characterize the chip kinematics. Results from the chip characterization studies indicate that the chip flow and final form show a remarkable consistency across multiple levels of workpiece and tool configurations as well as cutting conditions. A new tooling system is then designed to comprehensively break the chip by backward bending. Test results with the new tooling system prove that by utilizing the chip guidance and backward bending mechanism, long continuous chips can be more consistently broken into smaller segments that are generally deemed acceptable or good chips. It is found that the proposed tool can be applied effectively over a wider range of cutting conditions than present chip breakers thus taking possibly the first step towards achieving universal chip control in machining.