Sohn International Symposium ADVANCED PROCESSING OF METALS AND MATERIALS VOLUME 5 - NEW, IMPROVED AND EXISTING TECHNOLOGIES: IRON AND STEEL and RECYCLING AND WASTE TREATMENT Edited by F. Kongoli and R.G. Reddy TMS (The Minerals, Metals & Materials Society), 2006 EXPERIMENTAL ANALYSIS FOR THERMALLY NON-EQUILIBRIUM STATE UNDER MICROWAVE IRRADIATIONS A GREENER PROCESS FOR STEEL MAKING 1 Motoyasu Sato, 1Akihiro Matsubara, 1Sadatsugu Takayama, 1Shigeru Sudo 1Osamu Motojima, 2 Kazuhiro Nagata, 2Kotaro Ishizaki, 3Tetsuro Hayashi, 4 Dinesh Agrawal, 4 Rustum Roy 1 NIFS (National Institute for Fusion Science); 322-6 Oroshi,Toki,Gifu, 509-5292 Japan 2 Graduate School of Science and Engineering;Tokyo Institute Of Technology 3 Research Institute of Industrial Products Gifu Prefectural Government 1288 Ozeki, Seki-city, Gifu 501-3265 Japan 4 Materials Research Institute, Penn State University; University Park, PA 16802 USA Keywords: Carbon dioxide emission, Microwave Energy, Pig Iron, Thermally non-equilibrium Abstract Highly pure pig irons were produced in a multimode microwave reactor from powdered iron ores with carbon as a reducing agent in the nitrogen atmosphere. The grains in compacted powder absorb microwave energy selectively. Microwave-matter interaction creates thermal nonequilibrium state microscopically and enhances chemical reactions and the phase mixing at the grain boundaries very rapidly. The visible light spectroscopic techniques was used to monitor the progress of the reactions. Up to 650°C, the heated powders radiate the continuous spectrum of blackbody emission. The small non-equilibrium hot spots rise, move and finally burst in to brighter light emitting from all over the surface at 650°C. CN molecules and Fe (I ) atoms were identified in the recorded spectrum. These bursts are similar to the “ignition propagation” normally observed in chemical reactions. The line spectra originated from CO molecules have not been detected yet. The solid-solid reaction could be expected between the iron oxides and carbon to produce CO2 directly. A loss in the sample weight was accelerated during the excess-emission. These are the clear evidence that microwaves cause thermally non-equilibrium state and accelerate reduction process. The reduction of iron ore is completed at 1380°C and relatively very pure pig iron was produced. It should be noted that the impurity level of Mg, S, Si, P and Ti is only 5-10% of what is found in the pig irons produced by modern conventional blast furnaces in the steel industries. The necessary amount of carbon needed was 1/2 compared to conventional blast furnace to produce the unit weight of steel, if we applied renewable energy or nuclear power for the microwave excitations. Introduction As the Kyoto protocol come into effect, aggressive preservation of resources and energy savings are becoming progressively pressing needs for our country. However, the effectiveness of improvement of conventional industrial process is reaching its limits, hence calling for a new perspective to approach this problem. To put it on one extreme, the essence of civilization is to 157 produce, heat, and process materials. Since the beginning of industrialization, the process of heating has been based on the utilization of external heating sources via conduction, transmission, and radiation. Should this process be given a drastic change, the most effective energy saving can be achieved. Utilizing microwave energy for heating purposes has its distinctive characteristics in that it does not use an external heating source. Researchers in academia and industry have been working in the area of microwave processing of a variety of materials for many years. But what is new and unique about the present work is that for the first time the Penn State's experiments have shown that it can be applied as efficiently and effectively (if not more) to powdered metals as to the ceramic systems(1). Going further, there are even greater potential of the possibilities surrounding the exploitation of their radically different effects of the E and H components of the microwave electromagnetic field(2). Although many hypotheses have been presented through studies to investigate mechanism of microwave heating worldwide, no conclusive results have been presented to date. Using a digital microscope, we recorded a visual movie image in-situ observation of heating process of powder consisting Fe3O4 and BaCO3 by microwave(3)(4)(5). Random generation, movement, and disappearance of hot spots in the order of 100 micron were observed throughout duration of a few seconds. The temperature, size, shape, and the duration of the hot spots maintained certain regularity. This is the first case in the world of capturing formation of micron scale strong thermally non-equilibrium or localized temperature gradients (a few hundred oC/100 micron, a few thousand oC/mm) system during heating. In materials comprised of two compounds (even in multi compound system), occurrence of selective heating due to different microwave absorption rates of different phases, resulting in to a large temperature difference between the phases, is expected. This opens up the possibility of “field engineering” of most sophisticated value added electronic and optical materials. And also how localized an-isothermal situations in a microwave field can cause drastic enhancements in the reaction and diffusion kinetics. Nagata, et al of Tokyo Institute of Technology had been working on development of unique ultra high purity iron refinement technology that is based on ancient Japanese iron refinement method called "Tatara Process". The encounters with the report of microwave heating of powder metals gave them an idea that rapid reduction of iron should be possible by application of microwaves without relying on burning of carbon for de-oxidation. Joint experiments with NIFS et al proved that high purity iron (2% carbon density) with less than 1/10th of impurities, such as manganese, sulfur, phosphor, silicon, titanium, etc., as compared to irons from modern pile furnace can be produced in a short time, while reducing consumption of carbon to 1/2 (5) . This result developed into a new research theme of Suppressed CO2 Emission, Rapid Iron Refinement Method by Microwave Processing, which is aimed for reduction of several millions of tons of CO2 emission (per single pile furnace). The magnetite could be heated by the H-field of microwave and carbon by the E-field during the process. The amount of energy would be supplied by microwave for removing oxygen from magnetite. If the renewable energy, such as solar, hydro and nuclear power, is applied to generate microwave, it can reduce the emission of CO2 at least 50% of what is necessary in the conventional blast furnaces. The field in which microwave heating is effective in energy saving is in the high temperature region of 1000 oC to 2000 oC. Materials industries, such as metal refinery, steel production, sintering, and nanotechnology are among them. Application of microwaves in the iron industry, which is the backbone of these key industries, is the field where the greatest effect in reduction of carbon dioxide emission is expected. Iron ore refinement by means of pile furnace has utilized same basic structure based on the same principle for two hundred years. We have conducted a 158 series of experiments to prove effectiveness of rapid and high purity refinement under low temperature and high oxygen potential by means of microwave application, and achieved highly positive results. This paper provides the results achieved so far of this ongoing project. Experimental The experiments of reduction of iron oxide have been successfully conducted in a microwave batch furnace. The chamber of furnace is made of a stainless steel with hexagonal cross-section of 1.1m wide and 1.2m long that reduces the microwave energy concentration to the center of the cylinder. The metal rotators also scatter the standing mode in the chamber (Figure 1). The uniform heating in expected in the region of operation inside the chamber. Five magnetrons radiate 2.5~12.5 kW microwave at 2.45 GHz. The chamber was evacuated down to 0.1 Pa and refilled by nitrogen gas. Nitrogen is kept flowing at 2~5 litter/minutes at a little higher than the ambient pressure. The diagnostic systems were prepared to investigate the process under the thermally nonequilibrium reactions. The visible light spectrometer will detect the line spectrum overlapping to continuous spectra of the blackbody emissions. The combination of visible light spectrometer to the infrared pyrometer was the basic diagnostic tool. The system monitored in-situ the average temperatures and nonlinear excitations on the surface of the sample in the spot size of 10 mm. The entire process was monitored by high resolution video camera. Both the natural iron ore with coal and the purified reagent of Fe3O4 with graphite were prepared for the experiments. The iron ores milled into powders under 100P. The coal was under 50P. The grain sizes and the mixed weight ratios are listed in Table-1. The mixed powders were filled in a crucible with the tap density around 30%. The crucible was thermally insulated by the alumina-silica fiberboard. The insulation package containing the crucible installed in the microwave furnace as illustrated in figure-2. Fiber optics for spectrometer Infrared pyrometer Video camera Spectrometer Mode stair Thermal insulator Fig. 1. Pictures and the illustration of diagnostic system by visible lights 159 Grain size (P Pure Sample #1 Pure Sample #2 Pure Sample #3 Pure Sample #4 Fe3O4 50~100 Carbon 10 Fe3O4 : C Ratio Theoretical Value 2:1 Weight Mol 50 : 50 1 : 19.2 82 : 18 1 : 4.23 89 : 11 1:2 95 : 5 1:1 Remarks Expected products Fe3O4+2C = Fe + CO2 +2% FeC Fe3O4+C = 2FeO+ Fe Iron Ores #1 89 : 11 Table-1 Grain size and mixing ratio of magnetite and carbon of the samples Thermal Insulators 68 mm SiC plate for Hybrid Heating Figure-2 Heating unit filling up the sample in the crucible, Note: SiC plate was used only in an experiment of hybrid heating. Experiment (I) Microwave Processing of Fe304 Powder Mixed with Graphite of Equivalent Mol Concentration for the Reduction The first experiment was done using the sample with pure reagent of Fe3O4 and pure graphite powders that listed as the Sample#3 in table-1. The weight ratio of magnetite and graphite was 89:11. The amount of carbon was equivalent to the mol concentration for de-oxidation of the magnetite to pig iron that contained 2% carbon. Total weight of the sample and volume were 89.3g and 89 cc respectively. The applied power was 5kW. The temporal evolutions of line mission spectra, typical video pictures, infrared temperature and microwave output power were displayed respectively from top to the bottom in the figure-3. The process showed three steps: 1. RT to <690 °C, 2. Temperature jump from 690°C to 980°C in a few seconds and slower temperature rise to 1150°C. 3. Formation of the pig iron. The small drops appeared and agglomerated to larger drops. The slag was being released mechanically in the agglomeration. 160 Step I (Room Temperature ~ 600 oC) The microwave power was limited at 2.5 kW until the evaporation of combined water in the crystal. The heating rate began to slow down, but the temperature kept rising from 400 to 600 oC in 300 seconds. Small hot spots, less than 1 mm in diameter, blinked in the cracks on the surface of the sample as shown in the left two video pictures in figure 3. They became stronger and more frequent when the temperature closes to 690 oC. 4 T = 887OC, Mainly CN 4 T = 1262OC, Mainly Fe 4 3 3 3 2 2 2 1 1 1 T = 1438OC, Mainly Fe 0 0 0 370380390400410420430440 370380390400410420430440 370380390400410420430440 λ (nm) λ (nm) λ (nm) Step II Step I Step III Video Pictures 8000 800 Visible Light 80 8 Spectroscopy T ( C) O Microwave Power 100 200 300 400 500 600 700 800 900 1000 1100 time (sec) Figure –3 Line mission spectrums, typical video pictures, infrared temperature and microwave output power V.S. time 161 MW power (kW) IR Temperature 1600 1400 1200 1000 800 600 400 200 0 10 8 6 4 2 0 1200 QuickTimeý Dz YUV420 ÉRÅ[ÉfÉbÉN êLí£ÉvÉçÉOÉâÉÄ Ç™Ç±ÇÃÉsÉNÉ`ÉÉǾå©ÇÈǞǽDžÇÕïKóvÇ-Ç ÅB 378 sec QuickTimeý Dz YUV420 ÉRÅ[ÉfÉbÉN êLí£ÉvÉçÉOÉâÉÄ Ç™Ç±ÇÃÉsÉNÉ`ÉÉǾå©ÇÈǞǽDžÇÕïKóvÇ-Ç ÅB 378 + 0.2 sec QuickTimeý Dz YUV420 ÉRÅ[ÉfÉbÉN êLí£ÉvÉçÉOÉâÉÄ Ç™Ç±ÇÃÉsÉNÉ`ÉÉǾå©ÇÈǞǽDžÇÕïKóvÇ-Ç ÅB 379 + 1.2sec QuickTimeý Dz YUV420 ÉRÅ[ÉfÉbÉN êLí£ÉvÉçÉOÉâÉÄ Ç™Ç±ÇÃÉsÉNÉ`ÉÉǾå©ÇÈǞǽDžÇÕïKóvÇ-Ç ÅB QuickTimeý Dz YUV420 ÉRÅ[ÉfÉbÉN êLí£ÉvÉçÉOÉâÉÄ Ç™Ç±ÇÃÉsÉNÉ`ÉÉǾå©ÇÈǞǽDžÇÕïKóvÇ-Ç ÅB 380 +2.2 sec 378 +0.4 sec QuickTimeý Dz YUV420 ÉRÅ[ÉfÉbÉN êLí£ÉvÉçÉOÉâÉÄ Ç™Ç±ÇÃÉsÉNÉ`ÉÉǾå©ÇÈǞǽDžÇÕïKóvÇ-Ç ÅB 381 + 3 sec Figure 4. Ignition Propagation at 690 oC and temperature jump Step II (Temperature jump from 690 oC to 950 oC and de-oxidation up to 1350 oC ) At about 690 oC, as illustrated in figure 4, very bright discharge flashed and it extended to all over the sample surface in 0.1 seconds. Then in the next 2~3 seconds, the bright flame burst up and sparks sprayed out through a hole drilled on top of the insulator. It is not clear how deep the flash penetrates into the body of the sample. During the bursts, the temperature jumped to 950 o C. After the burst, it kept on rising from 950 oC to 1150 oC. The flame continues until the reaction is completed. The emissions of line spectra that consisted of carbon-nitride (CN) and Iron atoms (Fe I) were initiated at the burst. The CN decreased and disappeared in a few minutes. The emission by Fe(I) continued, while the CN lines decreased and disappeared in a few minutes. No emission lines of CO or CO2 were detected. The emission and flame disappeared when the microwave power was turned off. Step III Formation of Molten Metal The video showed that the surface of the sample became brighter during the process and the smaller. When the temperature reached to 1350 oC, molten metal appeared in the crucible as shown in figure-7. The visible light emissions idicated that the strongest peak was that of Fe(I). The excitation levels for them were estimated to be of several electron volts. It was much higher than the bulk kinetic energy of Fe atoms which is 1100 oC ( 0.1eV) by infrared pyrometer. It suggests that the thermally non-equilibrium state was excited by the microwave at the atomic level. 162 Experiment (II) Investigations for Optimum Quantity of Carbon Content All energy is supplied by the burning of carbons (cokes) in the conventional blast furnace. It is the most interested question “How much energy can be replaced by microwave irradiation?”. The samples with different weight ratios (mol concentrations) of magnetite and carbon were examined under the identical conditions of experimental setup and same microwave power. The samples were listed as the pure samples # 1 ~ #4 in the table-1. The atmosphere was nitrogen. The processes were observed by visible light spectrometer and video monitors. The phase composition of the products was investigated by XRD measurements. Pure sample #1 (50:50) It is very rich in carbon. The burst and temperature jump were not clear. CN line appeared at 700 o C, but no emission was observed from steel components. The excess unreacted carbon remained in the powder. Small drops, less than 1mm, were observed in the powders. The amount of the Fe was too small to detect. The XRD patterns show only the peaks of graphite. T = 990 0C (t = 472 sec) 3 CN 2.0x103 250 200 Profile of the spectra 1.5x103 150 1.0x103 CN 5.0x102 100 50 0.0 380 390 400 410 420 430 440 450 0 20 wavelength (nm) Fe 2.5x103 Graphite Intensity (a.u.) 3.0x10 30 40 50 60 1600 1400 ΔT = 2.9 oC / sec Δt O T ( C) 1200 1000 800 600 400 100 200 300 400 500 600 700 time (sec) Residual graphite powder with a bit of small iron balls CN appears continuously. Figure-5 Pure sample #1 (50:50) Experiment with very rich carbon Pure sample #2(82:18) The sample contained carbon almost twice for the reduction of magnetite in the sample. The burst and temperature jump occurred at 700 oC. The metal was produced showing peaks of Fe by XRD. But, the reduction was limited on the surface only in the crucible. The core of the sample remained in powders form. The weight of the produced metal was less than 20% of theoretical expectation. 163 T = 1030 0C (t = 804 sec) Fe 400 Fe 6.0x102 Fe Intensity (a.u.) 8.0x102 300 2 4.0x10 2.0x10 100 0.0 380 390 400 410 420 430 440 450 0 20 wavelength (nm) D 2006/03/02 20 53 D Graphite 200 2 30 40 50 60 k 20060222b i O T ( C) 1600 1400 1200 ΔT = 16 0C / sec Δt 1000 800 600 400 500 600 time (sec) 700 800 900 1000 1100 T-jump is clear. Fe and CN appear. Figure-6 Pure sample #2(82:18) The sample contained carbon twice for the reduction of magnetite Pure sample#3(89:11) This was the best. The products weight was 95% of the estimated weight. It is the stoichiometric carbon amount needed for complete reduction of the magnetite in the sample. These experiments were explained in the previous section. Figure –7 The highest yield and best quality Pig Irons by the microwave Pure samaple#4(95:5) It is the low carbon experiment. The amount of carbon is just a half of what is needed to complete reduction of the magnetite. Temperature jumps were observed. First jump was at 690 o C with CN light emission. The temperature rose to 800 oC and it has the second jump to 1000 o C. The emission of CN line did not show up. Only the Fe(I) lines were detected. The temperature increased up to 1400 oC and finally a big molten metal drop remained at the bottom of the crucible. The XRD shows that the major peaks were of FeO and Fe as a minor phase. 164 1.2x103 1.0x103 Fe 3000 Fe 2 8.0x10 FeO T = 890 0C (t = 494 sec) 2500 6.0x102 2000 4.0x102 1500 1600 1400 O T ( C) 1200 1000 390 400 410 420 430 440 450 FeO 0.0 380 500 0 20 ΔT = 300 C / sec Δt 30 40 Fe 2.0x102 50 60 1000 ΔT = 14 0C / sec Δt 800 600 400 200 300 400 500 600 700 800 time (sec) Almost iron spectra. The frame flashes, on the same time temperature goes up and down. Figure-7 Pure samaple#4 (95:5) Poor carbon experiment. The amount of carbon is just a half to de-oxide the magnetite in the sample. Experiment (III) Reduction of Natural Iron Ores in the Microwave Blast Furnace The reductions of natural iron ores were examined in the microwave blast furnace. The natural ore was the loadstone produced from Romeral Chili. It is the high quality ore containing magnetite more than 90%. It was grinded to less than 100P. It was mixed with powdered natural coal with the weight ratio of 81:11 in accordance with the experiments mentioned above. The weight of the sample was 1kg. Microwave power was kept in the range 5~7.5 kW. The atmosphere was nitrogen. The experiment showed almost identical steps of pure magnetite/ carbon compound with 89:11. The burst and temperature jump appeared at about 700 oC. The yellow colored flame was seen more clearly than the pure regent, because natural powders contained more Sodium. The video camera visualized the metal formation process. About 1mm diameter metal drops appeared in the powder, when the temperature exceeded 1150oC that was the melting temperature of the pig iron containing 2% carbon. The drops became larger in the next 10 minutes as big as 5~8 mm diameter. They sunk into the powder by the gravity. New small drops were born on the fresh powder and process repeated itself. The growth rate increased with the temperature. Finally, almost all the powder was reduced to the metal at 1380oC. The reduction process finished at 1380°C and the very pure pig iron was produced. The level of the impurities such as Mg, S, Si, P and Ti, were only 10-20% of the levels normally observed in the pig irons supplied by conventional blast furnaces, as shown in Figure–8. The weight of pig iron was 530 grams. Assuming the ore contained 100% of magnetite, 638 gram of pig iron would be produced. The product weight was about 85 % of the ideal value. 165 çÇèÉìxê òB Impurity Contents 0.12 0.1 Åì 0.08 ånóÒ1 Inside 1 ånóÒ2 Inside 2 ånóÒ3 Inside 3 ånóÒ4 surface 0.06 0.04 0.02 0 Mn S Si Ti ïsèÉï® Figure-8 Impurity in the Pig Iron By Microwave Reduction Discussions Optimized carbon content for microwave blast furnace The series of our experiments show clearly in the microwave blast furnace that; 1) The amount of carbon must satisfy the chemical equation; Fe3O4 + 2 C = 3 Fe + 2CO2 –75.66 kcal/mol. 2) The energy is supplied by microwave irradiation for heating powders and for making up the difference of enthalpies between the iron oxide and carbon dioxide (–75.66 kcal/mol). 3) Carbon played only just as a reducing agent. 4) Pig iron was produce uniformly from the surface to the core of the sample mixed with carbon at the optimized mol ratio. The product remains at the stage of FeO in case of insufficient carbon. 5) The maximum temperature was 1380 oC to finish the reduction and to get liquid pig iron. 6) The impurity contents were 1/10 compared to the products by conventional blast furnace. An innovation by microwave blast furnace is proposed here that the exhaust of CO2 can be reduced almost one half in comparison of the existing blast furnaces, if the energy could be supplied to microwave generators that is powered by the renewable energy or nuclear power plants. Our experiments make it clear that the penetration depth of the microwave is deep enough to operate the microwave blast furnace in the industrial scale. 166 The innovation would be highly possible from the viewpoint of engineering. The next step must be the demonstration of designing and building a larger scale microwave blast furnace appealing to the steel industries. Re-configuring the Science of Materials Synthesis/Reactions Scientific interest in our results is more profound than mere heating mechanism of powders by microwaves. Classical chemistry considers the general reaction of say A+B C+D Reactants Products by considering the free energy of the reactants and products, as these are varied by changing the intensive variables – usually limited to temperature (T) and pressure (P). The equilibrium can be shifted from one side to other; and the stable phases determined under specific selected conditions, etc. The classic thermodynamic approach, that is Electric field - Plasma (Electrons) – Material, is tried to explain an energy transfer mechanism. As the emission spectra of Fe (I) were the result of electron impact excitation, the flame should contain electrons and ions in the neutral gas composed of CO am/or CO2. The microwave electric field coupled to the kinetic energy of the electrons and dissipated into CO and /or CO2 molecules through the collision process. It also excited and vaporized Fe atoms from the surface layer of each grain of iron oxide by collisions. In the chemical reaction, the hot CO or CO2 gas transfers the heat to the reactant. Higher the temperature of the gas is, larger the heat flux from gas to the reactants. Microwave assists to heat up the gas more rapidly than by the burning of the carbon only. If the characteristic times of the chemical reduction were longer than the period of thermalization, the chemical reaction could be expected under the equilibrium state. This approach is, of course, valid very generally if the temperature is caused exclusively by phonon excitation alone (which to date has been the only condition considered in thermodynamics). It is therefore self-evident that ALL equilibria in ALL chemical reactions will be affected (to a greater or lesser extent) when the radiation can affect the electronic structure of the phase, in any way other than through the kT thermal energy. The next step in understanding then becomes the issue of how does the magnetic (or electric) field couple to the crystalline phase and how does it create the excited state noted above. According to a standard textbook on interaction of microwaves with matter the microwave 3 power absorbed per unit volume (P in W/m ) is expressed by the equation: P = SfRH0H"( PP"+ where E and H are the electric and magnetic fields, f0 is the frequency, H" & P" dielectric and magnetic loss factors respectively. However, in the vast literature on theories of microwavematter interaction, the magnetic field effects have been totally ignored. Our experimental results already demand a major theoretical change. Magnetic fields do interact with matter and have profound effects. Microwave energy coupling to the unpaired spins in the material is the key for the chain reaction. The following experiment suggests that the direct energy conversion from electromagnetic wave to material. A paving plate made of SiC was inserted at the bottom of the crucible as shown in 167 figure-2. The part of the microwave energy was converted to thermal energy in the paving and the sample was heated by conduction. The temperature rise of the surface by conduction was identical to the pure microwave up to 700°C, however, neither temperature jump nor burst appeared. The temperature saturated at 1000°C and the reduction of iron was very low. The burst and jump were particular nonlinear phenomena depending on the microwave power. The threshold was determined by the intensity of electromagnetic wave. In our experimental conditions, the threshold powers were 2.5kW without the paving and more tan 12.5 kW with paving. These experiments clearly show that the microwave electric and magnetic field supplied the energy directly to the material to make chemical process, such as reduction and heating. The burst itself and the high-temperature state after burst were sustained by the microwave power. The equilibrium lines cross over at 690°C for carbon- carbon oxides and for Iron oxide on the diagram of free energies V.S. temperatures (Ellinghum Diagram) as shown in figure-10. The reaction can be separate at this point to the Step I and to Step II/III in figure-3. Below this temperature, line emissions were not observed on the sample. The localized sparks were triggered by the electric field of microwave. When the temperature reached to higher than the cross point, a spark ignited the burst as shown in figure-4. The chemical reactions induced locally both the reduction of iron oxide and the oxidation of the carbon (combustion) in the spot. The non-equilibrium state was excited and the reductions were enhanced by microwave. The oxidation of carbon gave the thermal energy to the near particles on a microscopic scale. When the microwave + (microscopically) thermal energy transfer exceeds the enthalpy of the iron oxide, it gives oxygen to the other carbon. The carbon then heats the next iron oxide. When the input power of microwave is turned off, the emission-light disappeared in a moment and the temperature rapidly decreased independently of the temperature. In case of conventional furnace, that supplies the energy only by the burning of carbon, the process continued but very gently. The role of the microwave is crucial for the present rapid phenomenon. It has been now shown in the series of experiments (here and on a wide range of materials, Si, TiO2, ferrites etc.) that microwave radiation simultaneously can cause a solid material to both have its temperature raised, and to be transformed to an electronically (and hence thermodynamically) excited state. i.e. Atº + hȣ (2.45GHz) = A*t1 Moreover, the figures and summaries of our data clearly demonstrate that: A + hȣE (2.45GHz) = A*E and A + hȣH = A*H and further that A*E  A*H In a qualitative way we can be sure that the differences only in the field (E or H) must be responsible for the data. Reviewing our experimental results here, the excitation levels were estimated to be several electron volts corresponding to the line emissions. On the other hand, the infrared pyrometer 168 indicated 950 oC that corresponded to 0.08eV. The existence of two different energy levels suggest that the thermally non-equilibrium state was excited at the atomic level. It is not able to distinguish the influence of the electric and magnetic field to the reactant in the multimode cavity used in the steel making experiments. However, according to our previous experiments using single mode cavity (2), carbon can be heated only in E-field and magnetite can be heated more effectively in the magnetic field. As the carbon is electrically conductive material, the current limit the penetration of microwave to the powders. If the carbon burned to CO or CO2 gas, microwave can penetrate deeper in to the powders through the remaining spaces between the grains of magnetite powders. The H-field heats up the magnetite more rapidly. It wakes up the temperature jump and burst. The reaction speed increased. This is the other considerable mechanism that does not depend on the thermodynamic equilibrium condition. In the assumption, microwave directly couples to the irons. The energy transfer efficiency is expected to be better than the pass through the kinetic energy of the electrons in the surface gas or plasma. Quantitative research must be done to clear the mechanism of microwave steel making. Figure –10 Reaction Free Energy V.S. Temperature (Ellingham Diagram) of iron oxide 169 Acknowledgement The research of visible light spectrum measurements has been supported by NIFS fund No10204014KYAI001 and supported by Kansai Electric Power Co. Inc Japan. The research of Prof Nagata has been supported by JSPS Category (s). The research of Profs. Roy and Agrawal has been supported by the Office of Naval Research. References (1) R.Roy, D. Agrawal, S. Gedevanishvili J. Cheng; Nature 399~668, (1999) (2) R.Roy, R.Peelamedu, L.Hutt, J.Cheng, D, Agrawal: “Definitive experimental evidence for microwave effects: radically new effects of separated E and H fields”, Mat Res Innovation 6 (2002) p128-140 (3) M. Sato, R. Roy, P. Ramesh, D.Agrawall:”Microscopic Non-equilibrium Heating - A Possible Mechanism of Microwave Effects” Proc. 4th International Symposium on Microwave Science and Its Application to Related Fields, 2004 (4) M.Sato, A.Matsubara, K.Kawahata, O.Motojima, T.Hayashi, S. Takayama, “Microscopically In-situ Investigation for Microwave” Processing of Metals by Visible Light Spectroscopy, Proc. 11th International Conference on Microwave and High Frequency Heating, O-24, Sep.11-15, 2005 Italy (5) Kazuhiro NAGATA, Kotaro ISHIZAKI and Tetsuro HAYASHI, Low temperature production of pig iron from carbon – composite pellets heated by microwave, 5th JapanBrazil Symposium on dust processing-energy-environment in metallurgical industries proceedings, Volume 1, pp 617 - 625, September 2004 170
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