Principais aspectos da polimerização do 1,3-butadieno Principles aspects of butadiene 1,3 polymerization

Atualmente, há uma grande demanda pelo polibutadieno com alto teor de unidades 1,4-cis, devido às suas excelentes propriedades físicas, tais como alta resistência à abrasão, baixo desenvolvimento de calor, baixa resistência ao rolamento, maior resistência à tensão, alta resistência à fadiga, baixa histerese e alta resistência à fratura. Tais características fazem com que esse elastômero seja cada vez mais utilizado na indústria pneumática. Assim, este trabalho apresenta uma breve revisão sobre a polimerização do 1,3-butadieno com diferentes sistemas catalíticos, sendo os sistemas à base de lantanídeos o principal foco desta revisão, pois esses sistemas são os mais estereoespecíficos para a polimerização 1,4-cis do butadieno.<br>Nowadays, there is a great demand for polybutadiene with high contents of cis groups owing to its excellent physical properties, such as high abrasion resistance and low heat build up. These characteristics make this elastomer one of the most used in pneumatic industry. Thus, this paper presents a brief review about the 1,3-butadiene polymerization by different catalysts systems, with the systems based on lanthanides being the main focus, as they are the most stereospecific for cis-1,4 polymerization of butadiene

Polimerização 1,4 - cis de butadieno com o sistema catalítico tetracloreto de titânio/triisobutilalumínio/iodo 1,4 cis-Polymerization of butadiene by the catalyst system titanium tetrachloride/triisobutylaluminium/iodine

Foi utilizado o sistema catalítico tipo Ziegler-Natta modificado, constituído por TiCl4/I2/Al(i-Bu)3 para a síntese de polibutadieno com alto teor de unidades 1,4-cis. Foi estudada a influência da variação da composição do sistema catalítico e da temperatura reacional na atividade catalítica, no massa molar e na microestrutura do polibutadieno. Os polímeros foram caracterizados por espectroscopia na região do infravermelho, cromatografia por exclusão por tamanho e calorimetria diferencial de varredura. Foi obtido polibutadieno com até 92% de unidades 1,4-cis e baixo teor de gel. A massa molar ponderal média variou, com a composição do sistema catalítico e com a temperatura reacional, na faixa de 3 a 50 x 10(4) e a polidispersão variou na faixa de 1,8 a 3,3. A atividade catalítica máxima foi obtida para as razões molares Al/Ti = 5 e I2/Ti = 2.<br>A modified Ziegler-Natta type catalytic system consisting of TiCl4/I2/Al(i-Bu)3 was used to produce polybutadiene with high content of 1,4-cis repeating units. The influence of the catalytic system composition and temperature on the catalyst activity, molecular weight and microstructure of the polybutadiene was studied. The polymers were characterized by infrared spectroscopy and size exclusion chromatography. Polybutadiene with up to 92% of 1,4-cis repeating units and low gel content was produced. The polymer molecular weight was dependent on the catalytic system composition and reaction temperature. The weight-average molecular weight varied from 3 to 50 x 10(4); the molecular weight distribution was low, ranging, from 1.8 to 3.3. The maximum catalytic activity was achieved at molar ratios Al/Ti = 5 and I2/Ti = 2

Influência das características estruturais sobre a processabilidade do polibutadieno alto cis Influence of structural characteristics on the high-cis polybutadiene processability

Características físicas, tais como peso molecular, distribuição de peso molecular e ramificações, têm importância significativa na processabilidade do polibutadieno. Assim, deve haver um balanceamento dessas características a fim de se obter boas propriedades mecânicas e boa processabilidade. Este Trabalho apresenta uma breve revisão sobre a influência das características estruturais na processabilidade do polibutadieno produzido por diferentes sistemas catalíticos. São apresentadas também algumas técnicas encontradas na literatura para melhorar a processabilidade desse elastômero.<br>Physical characteristics, such as, molecular weight, molecular weight distribution and branching, have a significant influence on polybutadiene processability. Thus, a balance should exist in these characteristics for good mechanical properties and processability. This work brings a brief review of the influence of structural characteristics on the processability of polybutadiene produced by different catalyst systems. Also presented are some techniques from the literature aimed at improving processability of this elastomer

Real-time-capable prediction of temperature and density profiles in a tokamak using RAPTOR and a first-principle-based transport model

The RAPTOR code is a control-oriented core plasma profile simulator with various applications in control design and verification, discharge optimization and real-time plasma simulation. To date, RAPTOR was capable of simulating the evolution of poloidal flux and electron temperature using empirical transport models, and required the user to input assumptions on the other profiles and plasma parameters. We present an extension of the code to simulate the temperature evolution of both ions and electrons, as well as the particle density transport. A proof-of-principle neural-network emulation of the quasilinear gyrokinetic QuaLiKiz transport model is coupled to RAPTOR for the calculation of first-principle-based heat and particle turbulent transport. These extended capabilities are demonstrated in a simulation of a JET discharge. The multi-channel simulation requires ∼0.2 s to simulate 1 second of a JET plasma, corresponding to ∼20 energy confinement times, while predicting experimental profiles within the limits of the transport model. The transport model requires no external inputs except for the boundary condition at the top of the H-mode pedestal. This marks the first time that simultaneous, accurate predictions of Te, Tiand nehave been obtained using a first-principle-based transport code that can run in faster-than-real-time for present-day tokamaks

Comparison of runaway electron generation parameters in small, medium-sized and large tokamaks - A survey of experiments in COMPASS, TCV, ASDEX-Upgrade and JET

This paper presents a survey of the experiments on runaway electrons (RE) carried out recently in frames of EUROFusion Consortium in different tokamaks: COMPASS, ASDEX-Upgrade, TCV and JET. Massive gas injection (MGI) has been used in different scenarios for RE generation in small and medium-sized tokamaks to elaborate the most efficient and reliable ones for future RE experiments. New data on RE generated at disruptions in COMPASS and ASDEX-Upgrade was collected and added to the JET database. Different accessible parameters of disruptions, such as current quench rate, conversion rate of plasma current into runaways, etc have been analysed for each tokamak and compared to JET data. It was shown, that tokamaks with larger geometrical sizes provide the wider limits for spatial and temporal variation of plasma parameters during disruptions, thus extending the parameter space for RE generation. The second part of experiments was dedicated to study of RE generation in stationary discharges in COMPASS, TCV and JET. Injection of Ne/Ar have been used to mock-up the JET MGI runaway suppression experiments. Secondary RE avalanching was identified and quantified for the first time in the TCV tokamak in RE generating discharges after massive Ne injection. Simulations of the primary RE generation and secondary avalanching dynamics in stationary discharges has demonstrated that RE current fraction created via avalanching could achieve up to 70-75% of the total plasma current in TCV. Relaxations which are reminiscent the phenomena associated to the kinetic instability driven by RE have been detected in RE discharges in TCV. Macroscopic parameters of RE dominating discharges in TCV before and after onset of the instability fit well to the empirical instability criterion, which was established in the early tokamaks and examined by results of recent numerical simulations

Runaway electron beam control

Post-disruption runaway electron (RE) beams in tokamaks with large current can cause deep melting of the vessel and are one of the major concerns for ITER operations. Consequently, a considerable effort is provided by the scientific community in order to test RE mitigation strategies. We present an overview of the results obtained at FTU and TCV controlling the current and position of RE beams to improve safety and repeatability of mitigation studies such as massive gas (MGI) and shattered pellet injections (SPI). We show that the proposed RE beam controller (REB-C) implemented at FTU and TCV is effective and that current reduction of the beam can be performed via the central solenoid reducing the energy of REs, providing an alternative/parallel mitigation strategy to MGI/SPI. Experimental results show that, meanwhile deuterium pellets injected on a fully formed RE beam are ablated but do not improve RE energy dissipation rate, heavy metals injected by a laser blow off system on low-density flat-top discharges with a high level of RE seeding seem to induce disruptions expelling REs. Instabilities during the RE beam plateau phase have shown to enhance losses of REs, expelled from the beam core. Then, with the aim of triggering instabilities to increase RE losses, an oscillating loop voltage has been tested on RE beam plateau phase at TCV revealing, for the first time, what seems to be a full conversion from runaway to ohmic current. We finally report progresses in the design of control strategies at JET in view of the incoming SPI mitigation experiments