Search results for: transition process.

Authors: Babak Saboori, Behzad Saboori, Johan S. Carlson, Rikard Söderberg

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As product life cycle becomes less and less every day, having flexible manufacturing processes for any companies seems more demanding. In the assembling of closures, i.e. opening parts in car body, hemming process is the one which needs more attention. This paper focused on the robot roller hemming process and how to reduce its cycle time by introducing a fast roller hemming process. A robot roller hemming process of a tailgate of Saab 93 SportCombi model is investigated as a case study in this paper. By applying task separation, robot coordination, and robot cell configuration principles in the roller hemming process, three alternatives are proposed, developed, and remarkable reduction in cycle times achieved [1].

Keywords: Cell configuration, cycle time, robot coordination, roller hemming.

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Authors: Sachin Man Bajimaya, SangChul Park, Gi-Nam Wang

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The objective of this paper is to estimate realistic principal extrusion process parameters by means of artificial neural network. Conventionally, finite element analysis is used to derive process parameters. However, the finite element analysis of the extrusion model does not consider the manufacturing process constraints in its modeling. Therefore, the process parameters obtained through such an analysis remains highly theoretical. Alternatively, process development in industrial extrusion is to a great extent based on trial and error and often involves full-size experiments, which are both expensive and time-consuming. The artificial neural network-based estimation of the extrusion process parameters prior to plant execution helps to make the actual extrusion operation more efficient because more realistic parameters may be obtained. And so, it bridges the gap between simulation and real manufacturing execution system. In this work, a suitable neural network is designed which is trained using an appropriate learning algorithm. The network so trained is used to predict the manufacturing process parameters.

Keywords: Artificial Neural Network (ANN), Indirect Extrusion, Finite Element Analysis, MES.

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Authors: P. Painmanakul, T. Chintateerachai, S. Lertlapwasin, N. Rojvilavan, T. Chalermsinsuwan, N. Chawaloesphonsiya, O. Larpparisudthi

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Conventional coagulation, advance oxidation process (AOPs), and the combined process were evaluated and compared for its suitability to treat the stabilized cutting-oil wastewater. The 90% efficiency was obtained from the coagulation at Al₂(SO₄)₃ dosage of 150 mg/L and pH 7. On the other hands, efficiencies of AOPs for 30 minutes oxidation time were 10% for acoustic oxidation, 12% for acoustic oxidation with hydrogen peroxide, 76% for Fenton, and 92% sono-Fenton processes. The highest efficiency for effective oil removal of AOPs required large amount of chemical. Therefore, AOPs were studied as a post-treatment after conventional separation process. The efficiency was considerable as the effluent COD can pass the standard required for industrial wastewater discharge with less chemical and energy consumption.

 

Keywords: Cutting oily-wastewater, Advance oxidation process, Sono-Fenton, Combined process.

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Authors: A. López–Vásquez, D. Santamaría, M. Tibatá, C. Gómez

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A study concerning the photocatalytic decolourization of Congo red (CR) dye, over artificial UV irradiation is presented. Photocatalysts based on a commercial titanium dioxide (TiO2) modified with transition metals (Ni, Cu and Zn) were used. The dopage method used was wet impregnation. A TiO2 sample without salt was subjected to the same hydrothermal treatment to be used as reference. Congo red solutions to several pH conditions (natural and basic) were used to evaluate photocatalytic performance of each doped catalysts. Photodecolourization percentage was measured spectrofotrometically after 3 h of treatment to 499 nm as response variable. Kinetics investigations of photodegradation indicated that reactions obey to Langmuir-Hinshelwood model and pseudo–first order law. The rate constant studies of photocatalytic decolourization reactions for Zn–TiO2 and Cu–TiO2 photocatalysts indicated that in all cases the rate constant of the reaction was higher than that of TiO2 undoped. These results show that nature of the metal modifying the TiO2 influence on the efficiency of the photocatalyst evaluated in process. Ni does not present an additional effect compared with TiO2, while Zn enhances the photoactivity due to its electronic properties.

Keywords: Congo red, Dopage, Photodecolourization, Titanium dioxide.

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Authors: Pakorn Traiprasertpong, Apichit Svang-Ariyaskul

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The production of ethyl tert-butyl ether (ETBE) was simulated through Aspen Plus. The objective of this work was to use the simulation results to be an alternative platform for ETBE production from naphtha cracking wastes for the industry to develop. ETBE is produced from isobutylene which is one of the wastes in naphtha cracking process. The content of isobutylene in the waste is less than 30% weight. The main part of this work was to propose a process to save the environment and to increase the product value by converting a great majority of the wastes into ETBE. Various processes were considered to determine the optimal production of ETBE. The proposed process increased ETBE production yield by 100% from conventional process with the purity of 96% weight. The results showed a great promise for developing this proposed process in an industrial scale.

Keywords: ETBE, process simulation, naphtha cracking, Aspen Plus

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Authors: Yina F. Muñoz, Alexander Paz, Hanns De La Fuente-Mella, Joaquin V. Fariña, Guilherme M. Sales

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The primary approach for estimating bridge deterioration uses Markov-chain models and regression analysis. Traditional Markov models have problems in estimating the required transition probabilities when a small sample size is used. Often, reliable bridge data have not been taken over large periods, thus large data sets may not be available. This study presents an important change to the traditional approach by using the Small Data Method to estimate transition probabilities. The results illustrate that the Small Data Method and traditional approach both provide similar estimates; however, the former method provides results that are more conservative. That is, Small Data Method provided slightly lower than expected bridge condition ratings compared with the traditional approach. Considering that bridges are critical infrastructures, the Small Data Method, which uses more information and provides more conservative estimates, may be more appropriate when the available sample size is small. In addition, regression analysis was used to calculate bridge deterioration. Condition ratings were determined for bridge groups, and the best regression model was selected for each group. The results obtained were very similar to those obtained when using Markov chains; however, it is desirable to use more data for better results.

Keywords: Concrete bridges, deterioration, Markov chains, probability matrix.

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Authors: Shiva Abdoli, Daniel T. Semere

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Several researches have been conducted to study consumption of energy in cutting process. Most of these researches are focusing to measure the consumption and propose consumption reduction methods. In this work, the relation between the cutting parameters and the consumption is investigated in order to establish a generalized energy consumption model that can be used for process and production planning in real production lines. Using the generalized model, the process planning will be carried out by taking into account the energy as a function of the selected process parameters. Similarly, the generalized model can be used in production planning to select the right operational parameters like batch sizes, routing, buffer size, etc. in a production line. The description and derivation of the model as well as a case study are given in this paper to illustrate the applicability and validity of the model.

Keywords: Process parameters, cutting process, energy efficiency, Material Removal Rate (MRR).

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Authors: M. Haddadzade, M. R. Razfar, M. Farahnakian

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Integration of process planning and scheduling functions is necessary to achieve superior overall system performance. This paper proposes a methodology for integration of process planning and scheduling for prismatic component that can be implemented in a company with existing departments. The developed model considers technological constraints whereas available time for machining in shop floor is the limiting factor to produce multiple process plan (MPP). It takes advantage of MPP while guarantied the fulfillment of the due dates via using overtime. This study has been proposed to determinate machining parameters, tools, machine and amount of over time within the minimum cost objective while overtime is considered for this. At last the illustration shows that the system performance is improved by as measured by cost and compatible with due date.

Keywords: Due date, Integration, Multiple process plan, Process planning, Scheduling.

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Authors: Yendiyarov Sergei, Zobnin Boris, Petrushenko Sergei

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Usually, the solid-fuel flow of an iron ore sinter plant consists of different types of the solid-fuels, which differ from each other. Information about the composition of the solid-fuel flow usually comes every 8-24 hours. It can be clearly seen that this information cannot be used to control the sintering process in real time. Due to this, we propose an expert system which uses indirect measurements from the process in order to obtain the composition of the solid-fuel flow by solving an optimization task. Then this information can be used to control the sintering process. The proposed technique can be successfully used to improve sinter quality and reduce the amount of solid-fuel used by the process.

Keywords: sintering process, particle swarm optimization, optimal control, expert system, solid-fuel

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Authors: Boonsrimuang P., Numsomran A., Kangwanrat S.

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The typical coupled-tanks process that is TITO plant has the difficulty in controller design because changing of system dynamics and interacting of process. This paper presents design methodology of auto-adjustable PI controller using MRAC technique. The proposed method can adjust the controller parameters in response to changes in plant and disturbance real time by referring to the reference model that specifies properties of the desired control system.

Keywords: PI controller, MRAC, Couple-tanks process

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Authors: P. Georgieva, S. Feyo de Azevedo

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This paper is focused on issues of process modeling and two model based control strategies of a fed-batch sugar crystallization process applying the concept of artificial neural networks (ANNs). The control objective is to force the operation into following optimal supersaturation trajectory. It is achieved by manipulating the feed flow rate of sugar liquor/syrup, considered as the control input. The control task is rather challenging due to the strong nonlinearity of the process dynamics and variations in the crystallization kinetics. Two control alternatives are considered – model predictive control (MPC) and feedback linearizing control (FLC). Adequate ANN process models are first built as part of the controller structures. MPC algorithm outperforms the FLC approach with respect to satisfactory reference tracking and smooth control action. However, the MPC is computationally much more involved since it requires an online numerical optimization, while for the FLC an analytical control solution was determined.

Keywords: artificial neural networks, nonlinear model control, process identification, crystallization process

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Authors: Mario Mastriani, Marcelo Naiouf

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The Gram-Schmidt Process (GSP) is used to convert a non-orthogonal basis (a set of linearly independent vectors) into an orthonormal basis (a set of orthogonal, unit-length vectors). The process consists of taking each vector and then subtracting the elements in common with the previous vectors. This paper introduces an Enhanced version of the Gram-Schmidt Process (EGSP) with inverse, which is useful for signal and image processing applications.

Keywords: Digital filters, digital signal and image processing, Gram-Schmidt Process, orthonormalization.

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Authors: Somkiat Tangjitsitcharoen, Siripong Damrongthaveesak

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This paper presents an advance in monitoring and process control of surface roughness in CNC machine for the turning and milling processes. An integration of the in-process monitoring and process control of the surface roughness is proposed and developed during the machining process by using the cutting force ratio. The previously developed surface roughness models for turning and milling processes of the author are adopted to predict the inprocess surface roughness, which consist of the cutting speed, the feed rate, the tool nose radius, the depth of cut, the rake angle, and the cutting force ratio. The cutting force ratios obtained from the turning and the milling are utilized to estimate the in-process surface roughness. The dynamometers are installed on the tool turret of CNC turning machine and the table of 5-axis machining center to monitor the cutting forces. The in-process control of the surface roughness has been developed and proposed to control the predicted surface roughness. It has been proved by the cutting tests that the proposed integration system of the in-process monitoring and the process control can be used to check the surface roughness during the cutting by utilizing the cutting force ratio.

Keywords: Turning, milling, monitoring, surface roughness, cutting force ratio.

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Authors: Abbas Al-Refaie

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This paper aims at improving the performance of the tableting process using statistical quality control and fuzzy goal programming. The tableting process was studied. Statistical control tools were used to characterize the existing process for three critical responses including the averages of a tablet’s weight, hardness, and thickness. At initial process factor settings, the estimated process capability index values for the tablet’s averages of weight, hardness, and thickness were 0.58, 3.36, and 0.88, respectively. The L₉ array was utilized to provide experimentation design. Fuzzy goal programming was then employed to find the combination of optimal factor settings. Optimization results showed that the process capability index values for a tablet’s averages of weight, hardness, and thickness were improved to 1.03, 4.42, and 1.42, respectively. Such improvements resulted in significant savings in quality and production costs.

Keywords: Fuzzy goal programming, control charts, process capability, tablet optimization.

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Authors: S. Beyou, B. Grondin-Perez, M. Benne, C. Damour, J.-P. Chabriat

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The industrial process of the sugar cane crystallization produces a residual that still contains a lot of soluble sucrose and the objective of the factory is to improve its extraction. Therefore, there are substantial losses justifying the search for the optimization of the process. Crystallization process studied on the industrial site is based on the “three massecuites process". The third step of this process constitutes the final stage of exhaustion of the sucrose dissolved in the mother liquor. During the process of the third step of crystallization (Ccrystallization), the phase that is studied and whose control is to be improved, is the growing phase (crystal growth phase). The study of this process on the industrial site is a problem in its own. A control scheme is proposed to improve the standard PID control law used in the factory. An auto-tuning PID controller based on instantaneous linearization of a neural network is then proposed.

Keywords: Auto-tuning, PID, Instantaneous linearization, Neural network, Non linear process, C-crystallisation.

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Authors: C. Patrascioiu, M. Jamali

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The paper deals with the simulation of the crude distillation process using the Unisim Design simulator. The necessity of simulating this process is argued both by considerations related to the design of the crude distillation column, but also by considerations related to the design of advanced control systems. In order to use the Unisim Design simulator to simulate the crude distillation process, the identification of the simulators used in Romania and an analysis of the PRO/II, HYSYS, and Aspen HYSYS simulators were carried out. Analysis of the simulators for the crude distillation process has allowed the authors to elaborate the conclusions of the success of the crude modelling. A first aspect developed by the authors is the implementation of specific problems of petroleum liquid-vapors equilibrium using Unisim Design simulator. The second major element of the article is the development of the methodology and the elaboration of the simulation program for the crude distillation process, using Unisim Design resources. The obtained results validate the proposed methodology and will allow dynamic simulation of the process.  

Keywords: Crude oil, distillation, simulation, Unisim Design, simulators.

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Authors: Larysa Novak-Kalyayeva, Aleksander Kuczabski, Orystlava Sydorchuk, Nataliia Fersman, Tatyana Zemlinskaia

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The article presents the results of the creative analysis and comparison of trends in the development of the theory of public administration during the period from the second half of the 20^th to the beginning of the 21^st century. The process of conceptualization of the priorities of public administration in the dynamics of reforming was held under the influence of such factors as globalization, integration, information and technological changes and human rights is examined. The priorities of the social state in the concepts of the second half of the 20^th century are studied. Peculiar approaches to determining the priorities of public administration in the countries of "Soviet dictatorship" in Central and Eastern Europe in the same period are outlined. Particular attention is paid to the priorities of public administration regarding the interaction between public power and society and the development of conceptual foundations for the modern managerial process. There is a thought that the dynamics of the formation of concepts of the European governance is characterized by the sequence of priorities: from socio-economic and moral-ethical to organizational-procedural and non-hierarchical ones. The priorities of the "welfare state" were focused on the decent level of material wellbeing of population. At the same time, the conception of "minimal state" emphasized priorities of human responsibility for their own fate under the conditions of minimal state protection. Later on, the emphasis was placed on horizontal ties and redistribution of powers and competences of "effective state" with its developed procedures and limits of responsibility at all levels of government and in close cooperation with the civil society. The priorities of the contemporary period are concentrated on human rights in the concepts of "good governance" and all the following ones, which recognize the absolute priority of public administration with compliance, provision and protection of human rights. There is a proved point of view that civilizational changes taking place under the influence of information and technological imperatives also stipulate changes in priorities, redistribution of emphases and update principles of managerial concepts on the basis of publicity, transparency, departure from traditional forms of hierarchy and control in favor of interactivity and inter-sectoral interaction, decentralization and humanization of managerial processes. The necessity to permanently carry out the reorganization, by establishing the interaction between different participants of public power and social relations, to establish a balance between political forces and social interests on the basis of mutual trust and mutual understanding determines changes of social, political, economic and humanitarian paradigms of public administration and their theoretical comprehension. The further studies of theoretical foundations of modern public administration in interdisciplinary discourse in the context of ambiguous consequences of the globalizational and integrational processes of modern European state-building would be advisable. This is especially true during the period of political transformations and economic crises which are the characteristic of the contemporary Europe, especially for democratic transition countries.

Keywords: Concepts of public administration, democratic transition countries, human rights, the priorities of public administration, theory of public administration.

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Authors: Wararat Rungworawut, Twittie Senivongse

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Business process model describes process flow of a business and can be seen as the requirement for developing a software application. This paper discusses a BPM2CD guideline which complements the Model Driven Architecture concept by suggesting how to create a platform-independent software model in the form of a UML class diagram from a business process model. An important step is the identification of UML classes from the business process model. A technique for object-oriented analysis called domain analysis is borrowed and key concepts in the business process model will be discovered and proposed as candidate classes for the class diagram. The paper enhances this step by using ontology search to help identify important classes for the business domain. As ontology is a source of knowledge for a particular domain which itself can link to ontologies of related domains, the search can give a refined set of candidate classes for the resulting class diagram.

Keywords: Business Process Model, Model DrivenArchitecture, Ontology, UML Class Diagram.

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Authors: Petia Georgieva, Sebastião Feyo de Azevedo

Abstract:

This paper is focused on issues of nonlinear dynamic process modeling and model-based predictive control of a fed-batch sugar crystallization process applying the concept of artificial neural networks as computational tools. The control objective is to force the operation into following optimal supersaturation trajectory. It is achieved by manipulating the feed flow rate of sugar liquor/syrup, considered as the control input. A feed forward neural network (FFNN) model of the process is first built as part of the controller structure to predict the process response over a specified (prediction) horizon. The predictions are supplied to an optimization procedure to determine the values of the control action over a specified (control) horizon that minimizes a predefined performance index. The control task is rather challenging due to the strong nonlinearity of the process dynamics and variations in the crystallization kinetics. However, the simulation results demonstrated smooth behavior of the control actions and satisfactory reference tracking.

Keywords: Feed forward neural network, process modelling, model predictive control, crystallization process.

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Authors: Mesbah. M. Salem, Mohamed. H. Elhsnawi, Saleh B. Mohamed

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An experimental investigation was conducted to study the effect of surface roughness on friction factor and heat transfer characteristics in single-phase fluid flow in a stainless steel micro-tube having diameter of 0.85 mm and average internal surface roughness of 1.7 μm with relative surface roughness of 0.002. Distilled water and R134a liquids were used as the working fluids and testing was conducted with Reynolds numbers ranging from 100 to 10,000 covering laminar, transition and turbulent flow conditions. The experiments were conducted with the micro-tube oriented horizontally with uniform heat fluxes applied at the test section. The results indicated that the friction factor of both water and R134a can be predicted by the Hagen-Poiseuille equation for laminar flow and the modified Miller correlation for turbulent flow and early transition from laminar to turbulent flows. The heat transfer results of water and R134a were in good agreement with the conventional theory in the laminar flow region and lower than the Adam’s correlation for turbulent flow region which deviates from conventional theory.

Keywords: Pressure drop, heat transfer, distilled water, R134a, micro-tube, laminar and turbulent flow.

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Authors: A. Youseef, F. Liu

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The existing information system (IS) developments methods are not met the requirements to resolve the security related IS problems and they fail to provide a successful integration of security and systems engineering during all development process stages. Hence, the security should be considered during the whole software development process and identified with the requirements specification. This paper aims to propose an integrated security and IS engineering approach in all software development process stages by using i* language. This proposed framework categorizes into three separate parts: modelling business environment part, modelling information technology system part and modelling IS security part. The results show that considering security IS goals in the whole system development process can have a positive influence on system implementation and better meet business expectations.

Keywords: Business Process Modelling (BPM), Information System Security, Software Development Process, Requirement Engineering.

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Authors: Eva Štěpánková

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The decision-making process is theoretically clearly defined. Generally, it includes the problem identification and analysis, data gathering, goals and criteria setting, alternatives development and optimal alternative choice and its implementation. In practice however, various modifications of the theoretical decision-making process can occur. The managers can consider some of the phases to be too complicated or unfeasible and thus they do not carry them out and conversely some of the steps can be overestimated. The aim of the paper is to reveal and characterize the perception of the individual phases of decision-making process by the managers. The research is concerned with managers in the military environment – commanders. Quantitative survey is focused cross-sectionally in the individual levels of management of the Ministry of Defence of the Czech Republic. On the total number of 135 respondents the analysis focuses on which of the decision-making process phases are problematic or not carried out in practice and which are again perceived to be the easiest. Then it is examined the reasons of the findings.

Keywords: Decision making, decision making process, decision problems.

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Authors: Sh. Arzani, H. Kazemi Esfeh, Y. Galeh Zadeh, V. Akbari

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Ethylene dichloride is a colorless liquid with a smell like chloroform. EDC is classified in the simple hydrocarbon group which is obtained from chlorinating ethylene gas. Its chemical formula is C2H2Cl2 which is used as the main mediator in VCM production. Therefore, the purification process of EDC is important in the petrochemical process. In this study, the purification unit of EDC was simulated, and then validation was performed. Finally, the impact of process parameter was studied for the degree of EDC purity. The results showed that by increasing the feed flow, the reflux impure combinations increase and result in an EDC purity decrease.

Keywords: Ethylene dichloride, purification, EDC, simulation.

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Authors: Seok Hong Min, Tae Kwon Ha

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With the increasing interest on Ti alloys, the extraction process of Ti from its typical ore, TiO₂, has long been and will be important issue. As an intermediate product for the production of pigment or titanium metal sponge, tetrachloride (TiCl₄) is produced by fluidized bed using high TiO₂ feedstock. The purity of TiCl₄ after chlorination is subjected to the quality of the titanium feedstock. Since the impurities in the TiCl₄ product are reported to final products, the purification process of the crude TiCl₄ is required. The purification process includes fractional distillation and chemical treatment, which depends on the nature of the impurities present and the required quality of the final product. In this study, thermodynamic analysis on the impurity effect in the chlorination process, which is the first step of extraction of Ti from TiO₂, has been conducted. All thermodynamic calculations were performed using the FactSage thermodynamical software.

Keywords: Rutile, titanium, chlorination process, impurities, thermodynamic calculation, FactSage.

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Authors: Jens Friedrich, Matthias A. Gebele, Armin Lechler, Alexander Verl

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Chatter vibrations and process instabilities are the most important factors limiting the productivity of the milling process. Chatter can leads to damage of the tool, the part or the machine tool. Therefore, the estimation and prediction of the process stability is very important. The process stability depends on the spindle speed, the depth of cut and the width of cut. In milling, the process conditions are defined in the NC-program. While the spindle speed is directly coded in the NC-program, the depth and width of cut are unknown. This paper presents a new simulation based approach for the prediction of the depth and width of cut of a milling process. The prediction is based on a material removal simulation with an analytically represented tool shape and a multi-dexel approach for the workpiece. The new calculation method allows the direct estimation of the depth and width of cut, which are the influencing parameters of the process stability, instead of the removed volume as existing approaches do. The knowledge can be used to predict the stability of new, unknown parts. Moreover with an additional vibration sensor, the stability lobe diagram of a milling process can be estimated and improved based on the estimated depth and width of cut.

Keywords: Dexel, process stability, material removal, milling.

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Authors: Gonçalo G. Aleixo, Alexandra B. Tenera

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This work will provide a new perspective of exploring innovation thematic. It will reveal that radical and incremental innovations are complementary during the innovation life cycle and accomplished through distinct ways of developing new products. Each new product development process will be constructed according to the nature of each innovation and the state of the product development. This paper proposes the inclusion of the organizational function areas that influence new product's development on the new product development process.

Keywords: Cross-functional, Incremental Innovation, New Product development Process, Radical Innovation

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Authors: Marko Popovic

Abstract:

There are three possible effects of Special Theory of Relativity (STR) on a thermodynamic system. Planck and Einstein looked upon this process as isobaric; on the other hand Ott saw it as an adiabatic process. However plenty of logical reasons show that the process is isotherm. Our phenomenological consideration demonstrates that the temperature is invariant with Lorenz transformation. In that case process is isotherm, so volume and pressure are Lorentz covariant. If the process is isotherm the Boyles law is Lorentz invariant. Also equilibrium constant and Gibbs energy, activation energy, enthalpy entropy and extent of the reaction became Lorentz invariant.

Keywords: STR, relativistic temperature transformation, Boyle'slaw, equilibrium constant, Gibbs energy.

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Authors: Tomas Cechura, Michal Simon

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The aim of this paper is to create a proposal for determining the costs of logistics processes by using process-oriented calculation methods. The traditional approach is that logistics costs are part of manufacturing overhead which is usually calculated as a percentage surcharge. Therefore in the traditional approach it is not obvious where and in which activities costs were incurred. So it is impossible to trace logistics costs to products. Our point of view is trying to fix or at least improve this issue. Another benefit of applying the process approach is identification of logistics processes which are otherwise part of manufacturing overhead. In the first part this paper describes the development of process-oriented methods over time. The next part shows the possibility of implementing the process-oriented method called Prozesskostenrechnung to logistics processes. The conclusion summarizes advantages and disadvantages of using this method in logistics.

Keywords: Cost, logistics, calculation, process-oriented method.

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Authors: Débora N. Zambrano, Marina O. Gosatti, Leandro M. Dufou, Daniel A. Serrano, M. Mónica Guraya, Soledad Perez-Catán

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Nanoporous g-Al₂O₃ samples were synthesized via a sol-gel technique, introducing changes in the Yoldas´ method. The aim of the work was to achieve an effective control of the nanostructure properties and morphology of the final g-Al₂O₃. The influence of the reagent temperature during the hydrolysis was evaluated in case of water at 5 ºC and 98 ºC, and alkoxide at -18 ºC and room temperature. Sol-gel transitions were performed at 120 ºC and room temperature. All g-Al₂O₃ samples were characterized by X-ray diffraction, nitrogen adsorption and thermal analysis. Our results showed that temperature of both water and alkoxide has not much influence on the nanostructure of the final g-Al₂O₃, thus giving a structure very similar to that of samples obtained by the reference method as long as the reaction temperature above 75 ºC is reached soon enough. XRD characterization showed diffraction patterns corresponding to g-Al₂O₃ for all samples. Also BET specific area values (253-280 m²/g) were similar to those obtained by Yoldas’s original method. The temperature of the sol-gel transition does not affect the resulting sample structure, and crystalline boehmite particles were identified in all dried gels. We analyzed the reproducibility of the samples’ structure by preparing different samples under identical conditions; we found that performing the sol-gel transition at 120 ºC favors the production of more reproducible samples and also reduces significantly the time of the sol-gel reaction.

Keywords: Nanostructure alumina, boehmite, sol-gel technique, N2 adsorption/desorption isotherm, pore size distribution, BET area.

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Authors: K. Mondal, S. Talapatra, M. Terrones, S. Pokhrel, C. Frizzel, B. Sumpter, V. Meunier, A. L. Elias

Abstract:

Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H₂) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H₂, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.

Keywords: CNT, CO hydro-deoxygenation, DFT, liquid fuels, XPS, XTL.

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