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Elsevier Editorial System(tm) for Hydrometallurgy Manuscript Draft Manuscript Number: HYDROM-D-12-00382R2 Title: Microwave mediated precipitation

and aging of iron oxyhydroxides at low temperature for possible hydrometallurgical applications Article Type: Technical Note Keywords: Iron oxyhydroxides; Precipitation; Microwave aging Corresponding Author: Dr. R.P. Das, Ph.D Corresponding Author's Institution: HydroMet Proc First Author: R. Das Order of Authors: R. Das; Meng-nan Lu; R. P Das; Wei Li; Jinhui Peng; Li-bo Zhang Abstract: Abstract This preliminary study examined the role of microwave radiation on precipitation and aging of iron oxyhydroxides at 60 oC. It was observed that due to rapid heating under microwave, transformation of -10 hours. This is in contrast to the usual aging temperature of > 100 oC adopted in most conventional studies, and several days of aging. Besides rapid transformation, microwave helps forming nano particles, with crystallite size of ~60 nm as determined from x-ray diffractograms, and < 100 nm particles as observed under TEM. Rapid Fe2O3 without the formation of intermediate γ-Fe2O3. This study brought out the advantages of low temperature microwave assisted precipitation / aging as a low energy process to transform iron oxyhydroxides, with likely applications in slurry rheology, synthesis of nano particles, and adsorption. Keywords:iron oxyhydroxides, precipitation, microwave aging

Suggested Reviewers: Goutam Das Ph.D. Senior Research Scientist CSIRO, Australia. , CSIRO, Australia Goutam.Das@csiro.au

Aleks Nikoloski Ph.D. Senior lecturer, Murdoch University, Australia A.Nikoloski@murdoch.edu.au

Mamata Mohapatra Ph.D. Scientist, Hydrometallurgy, IMMT, Bhubaneswar mamatamohapatra@yahoo.com

Cover Letter

Ms. Ref. No.: HYDROM-D-12-00382R1 Title: Microwave mediated precipitation and aging of iron oxyhydroxides at low temperature for possible hydrometallurgical applications. February 3, 2013 Dear Prof Petersen, My co-authors and I are very grateful to the reviewers and you for your valuable comments. We specially like to thank the reviewers for their patience in dealing with this paper. I would be thankful, if you kindly consider publishing it as a technical note.

I am attaching a note explaining the manner in which I have responded to referees’ comments. I look forward to your decision on this modified manuscript. With best regards, Sincerely, Das

Appropriate corrections incorporated. A new schematic drawing of the microwave furnace is added. Authors should modify it. Format corrected Reviewer #2: The manuscript is hardly revised. Section 3. Some sentences do not have full stop at the end.4 in the first sentence. There is no sampling between 6-8 h.g. it is written that 'crystalline phase appeared after 6h' in the first sentence. in the text. The sentence is modified.2. however. 2.3: i) Fig 3 should be Fig.*Detailed Response to Reviewers Reviewer #1: The manuscript now reads well. The illustration of the microwave (MW) furnace including locations of sample and thermo-couples should be added to the manuscript. Section 3. 4 shows no peak other than two line ferrihydrite peaks. and the text is suitably modified. ii) 6h sample in Fig. Some minor corrections are required in the manuscript. Some comments are listed below. Correction incorporated. e. (1) The experimental section should be described to be able to conduct reproductive experiment. Information of MW irradiation. so it is really not known when actually crystalline phase appeared in this 2 h period. 1. 3. explanation should be based on 8 h sample. Ahmed et al. and there is no appropriate answer to the reviewers. power of MW (Not current [A] but power [W]).. . should be described in the manuscript. Therefore.2. 4. Write a sentence in 'Aging procedure' how samples were collected during aging period of 4-12 h. Corrected 5. Minor corrections required for some references to make it as per the recent format. continuous or pulse and single-mode or multi-mode.2: Give 'year' for ref. Author should check the recent publication for giving references in the reference list.

5 and a-Fe2O3 are observed at the same positions. it transforms to -Fe2O3 easily. . similar to -FeOOH – in contrast to red colour of -Fe2O3.5O2.0 software for xrd patterns. these phases cannot be distinguished by only XRD data. In this study. Estimation of BET surface area seems to be insufficient.5 phase and the -Fe2O3 phase in XRD patterns cannot be understood. Appropriate modifications in the text have been incorporated. This preliminary study has shown that microwave treatment generates high surface area. we observed that Fe1. The surface area was estimated as specified by Sing et al.5O2. We agree with the reviewer that additional supporting evidence is required to prove the presence of Fe1. (4) Because diffraction peaks of the Fe1.5O2.833 (OH)0. Some diffraction peaks of Fe1.833 (OH)0. It is non-stoichiometric Fe2O3 (Ahmad et al.833 (OH)0.5 phase were observed at the same positions as the -Fe2O3 phase. The estimation of crystallinity was made by using Jade 6.5O2.(2) Estimation of crystallinity seems to be insufficient. We plan to study this aspect in future.833 (OH)0. (3) Particle sizes estimated by XRD and TEM are inconsistent with the high surface areas of 350 m2/g.5O2.5 .5 was dark brown. Details of estimation procedure of crystallinity should be explained in the manuscript. Perhaps. On heating. The former is an intermediate product of dehydroxylation. it is due to rapid heating. namely I(crystalline)/(I(noncrystalline)+I(crystalline). not consistent with the particle size. Before N2 adsorption experiment. This standard software is based on the basic expression for crystallinity . specimen is usually pretreated under vacuum above 100C.5 peaks appeared in the beginning. and Wolska and Schwertmann). gradually vanishing with time . How the authors distinguish the Fe1.5O2.833 (OH)0. From our study we observed that Fe1. The second confirmation was from the colour of the powder. Hu et al. This preliminary study lacks such information. especially information of 100% crystalline standard samples of the Fe-O-H system should be descried. We agree with the reviewer.833 (OH)0. and finally -Fe2O3 peaks appearing in their place.

*Highlights (for review) Highlights Precipitation of iron hydroxide under ambient condition . TEM. TG. and BET – The -Fe2O3 formed after aging was of nano size – A low temperature method to prepare fine iron oxide particles. .Aging of the precipitate under microwave at 60 oC – Characterisation of the precipitate through XRD.

and several days of aging. Engineering Laboratory of Microwave Application and Equipment Technology. synthesis of nano particles. 3. Wei Li 1.Das1.P. and adsorption. Page 1 of 24 . Email: drrpdas@yahoo.P. R. Li-bo Zhang 1.2. Precipitation.4. It was observed that due to rapid heating under microwave. Hydromet Proc. Besides rapid transformation.5.2.*Manuscript Click here to view linked References Microwave mediated precipitation and aging of iron oxyhydroxides at low temperature 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 for possible hydrometallurgical applications Meng-nan Lu 1.3. Key Laboratory of Unconventional Metallurgy. Jin-hui Peng 1. Kunming 650093.4 1. This study brought out the advantages of low temperature microwave assisted precipitation / aging as a low energy process to transform iron oxyhydroxides. Bhubaneswar 751018. Rapid transformation also promotes formation of Fe2O3 without the formation of intermediate γ-Fe2O3. Keywords:Iron oxyhydroxides.3.2. State Key Laboratory Breeding Base of Complex Nonferrous Metal Resources Cleaning Utilization in Yunnan Province.3. 4.Das.2. China.4. 5. 2. Kunming University of Science and Technology. Microwave aging Corresponding author: R. and < 100 nm particles as observed under TEM. with crystallite size of ~60 nm as determined from x-ray diffractograms.3. This is in contrast to the usual aging temperature of > 100 oC adopted in most conventional studies. transformation of two line ferrihydrite to Fe2O3 takes place within 4 -10 hours. Faculty of Metallurgy and Energy Engineering.4. India Abstract This preliminary study examined the role of microwave radiation on precipitation and aging of iron oxyhydroxides at 60 oC. with likely applications in slurry rheology. microwave helps forming nano particles.com Telephone +91 9437011128. Ministry of Education.

γ). Microwave energy is transmitted as a frequency electromagnetic energy. and also the main products of underwater corrosion (Nagayama and Cohen. These substances are widely distributed in water. where thermal energy is delivered at the surface. Each of these generates products with characteristic properties.1mm. carrier for drug delivery. 2007). and boiling point retardation. 2005) by rapid heating. surface property. Several researchers have prepared iron oxides and oxyhydroxides by adopting a number of precipitation and de-hydroxylation techniques. Contrary to other forms of heating. and shorten the reaction time (Xiangyuan et al. β.3033Hz frequency and its wavelength range is 1m . 1991). microwave heating delivers thermal energy inside the body to be heated. rock and soil. Iron oxides and oxyhydroxides can be divided into Fe2O3 (α. then microwave can superheat it to 400 oC. high density recording media. These are the main components of iron rust. Microwave is electromagnetic wave with 324 . It can effectively accelerate the reaction rate. but it is too weak to break different chemical bonds (Slangen et al. If water is the solvent. ability to (i) impart unique microstructure and properties. Schwertmann and Cornell (1991) have identified 16 different kinds of iron oxides and oxyhydroxides. size. FeO etc. Application of microwave energy to materials has numerous advantages. Examples of application of microwave heating include drying of wood (Hansson. dehydroxylation Page 2 of 24 . namely. 2006). and association with other anions and cations (Mohapatra et al. FeOOH (α. 1998). pigments and catalyst preparation. Earth surface content of iron oxides and iron oxyhydroxides is fairly abundant. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Introduction Iron oxide and oxyhydroxides are important materials used in many areas. and (iii) reduced energy consumption during material production. Fe3O4. or γ). shape. semiconductor industry. as well as the methods to synthesise these. β. e. 1962) as well as steel passivation (Suter et al. 1997). Microwave heating often leads to hot spots. (ii) synthesise new materials. crystallinity. such as.g.1. adsorbents for anions and cations (Cherepy et al.

Materials and Method 2. because it operates below the boiling point of water. Microwave was also used for annealing six line ferrihydrite at 60 oC. TGA. 1984) A small number of published literatures are available on microwave synthesis of iron oxyhydroxides. 90 oC . (i) in improving the rheology of slurry. sintering of ceramics. In this preliminary study. and cations from aqueous system during transformation. 1998) at temperatures 65-100 oC. and at 120 oC (Burleson and Penn 2006) for improved homogeneity of goethite. and the role of heating time on phase transformation and particle size was monitored through XRD. e. (ii) in de-watering. TEM. Synthesis of the iron oxide/oxyhydroxide Page 3 of 24 . synthesis of zeolite (Slangen. The available literature has little information on the role of microwave in low temperature transformation of iron hydroxide precipitate.1. synthesis of hydroxy 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 apatite. 2009). 2002). In another study.g. and curing of cement (Agarwal. It will also have potential applications in mineral and hydrometallurgical industries. 2. and BET. (iii) in transforming the precipitate to incorporate different anions. iron hydroxide precipitates were treated with microwave energy at 60 oC. microwave hydrothermal technique was used at 190 oC to synthesize a range of iron oxide powders from ferrous sulphate and sodium hydroxide (Dhage et al. iron oxide/oxyhydroxide nanophases were synthesised at seven different temperatures from100 to 250 oC using pulsed microwaves. Acicular goethite–magnetite particles have been prepared by microwave-driven hydrolysis of an aqueous solution of ferric and ferrous salts (Wang et al.of minerals. In yet another study (Parsons et al. 1998). and (iv) in preparing low cost iron oxyhydroxide adsorbents for anions and cations. and also for better control of its particle size and shape. Such transformation is energy efficient.

The precipitate was then mixed with 100 mL of deionized water Page 4 of 24 .1 Precipitation 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Iron oxyhydroxide samples were prepared by adding 3M potassium hydroxide solution slowly (approximate rate: 1mL/min) to 1M. In another variation.1. These are: a. Microwave radiation: (1) The precipitate was exposed to microwave radiation at 60 oC for varying duration of time (4 to 12 hours). Normal method: The precipitate was aged in water bath at 60 oC for a pre-determined time (1 to 7 days). Next it was washed till it is free of chloride ion as indicated by AgCl. During addition. 2.1.0. for completing the precipitation. to obtain de-hydroxylated samples. Then the slurry with precipitate was kept at room temperature for 24 hours.2. to generate separate individual de-hydroxylated product (Sample M610). This precipitate was used for aging. the slurry was kept under microwave radiation for 12 hours for completing the precipitation. (Sample MW610). Washing was followed by filtration in a vacuum filter. This was done in lieu of holding it at room temperature for 24 hours. the solution was continuously stirred (at 400 rev/min) by a magnetic stirrer. No stirring was done at this stage. four different aging techniques were followed using three different methods. c. 100 mL ferric chloride solution until the pH reached 11. to obtain de-hydroxylated sample (Sample N602 in Table 1) b.1 A. (2) The precipitate was mixed with 100 mL of deionized water and subjected to microwave radiation at 60 oC for varying amount of time (4 to 12 hours).2 Ageing process In this study. Microwave assisted precipitation and aging of the precipitate: The precipitate was placed in microwave oven cavity for aging at 25 oC for 12 hours with an initial current of 1. as in earlier samples.

All the methods. (vi) Power consumption: In an average. are summarized in Table 1. and the ratings were 220 V and 20 A.and further exposed to microwave radiation at 60 oC for 4 to 12 hours. During microwave radiation. as described above. 2. (v) Sample location: The sample for radiation was placed in a flask. effective space in the furnace tube was about 150 cm3. which was covered One located about 2 cm in the sample.3.5kW continuously adjustable water-cooled magnetron. It was manufactured by the key laboratory of unconventional metallurgy in Kunming University of science and technology. and the other on the with insulated material. It operated under pulse and multi mode. Its technical parameters were: (i) Microwave System: 1. approximately 150 watts of power was consumed for each test. 2. a microwave high-temperature reactor was used (Figure 1). Microwave furnace In this study. a thermocouple was introduced from the top of the microwave cavity.2.3 Characterisation techniques 2. and the furnace volume was about 20 L.5 A. Microwave frequency was 2450 ± 50 MHz The dimensions of the furnace were 1200 × 1500 × 600 mm. the initial current was maintained at 2. supporting standard waveguide. After placing the flask in the furnace. (ii) Operating temperature: Maximum 1200 oC.1 XRD analysis Page 5 of 24 . (iii) Microwave tube: A vertical quartz tube (with porous partition). and ≤ 1000 oC for continuous use. to obtain 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 de-hydroxylated samples (Sample MM610). (iv) Thermo couple locations: side wall.

75 oC) using 99. Result and Discussion 3. 1985). 2006). The samples were first subjected to high pure helium desorption. 2. prior to nitrogen adsorption at 77 K (-195.1.0 analysis software for xrd patterns (Huang. The powder sample was mixed in absolute ethanol. 3.4 BET The pore structures of samples were analyzed using an auto-sorption instrument (Contador's AUTSOR-1). Scanning was done between 2values of 20° to 80° at a rate of 2°min-1. Between 15 and 25 mg of sample was heated at 20 oC /min in air from 20 oC to 1200 oC and traces for weight losses were analyzed as a function of temperature. 200mA).1 Characterisation 3.2 TGA Thermo gravimetric analysis was carried out using a NETZSCH 449F3. An appropriate amount of sample was gained by copper mesh with 75kV excitation voltage of transmission electron microscope. surface area and pore structure were determined (Sing et al.3 TEM A Hitachi H300 transmission electron microscope was used to observe particle morphology. and then dispersed using an ultrasonic dispersing unit.3. The sample crystallinity and Full Width at Half Magnitude (FWHM) were estimated from diffraction peaks by using Jade 6.2. 2. 2. By analyzing the adsorption isotherms.1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 A Rigaku X-ray diffraction unit (JDX.10P.3A) was used to generate XRD pattern of samples with Cu Kradiation (40kv.1 XRD Page 6 of 24 .3.99% liquid nitrogen at a relative pressure of 10-6.

and ellipsoidal shape. and in 8-10 hours. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 showed that the initial precipitates were totally amorphous hydroxide tending to crystallise first. The first one corresponds to transformation of metastable γ-Fe2O3 to α-Fe2O3.X-ray diffractograms of precipitated iron hydroxide . there were two exothermic peaks at ~ 540 oC.2 Method of aging. and perhaps will have better adsorption properties.3 TEM The transmission electron micrographs showed the ability of microwave radiation to produce nano size α-Fe2O3. which has a generalised chemical formula of Fe2O3. the study did not show any distinct difference between the samples prepared under different microwave conditions. Next. Figures 2-5. 2011). and the duration of microwave radiation. the first one for physically combined water (at <100 oC) . and at ~790 oC. 1995). The results from the present study (Figure 6) showed the formation of α-Fe2O3 nano particles of <100 nm size.4 BET As presented in Table 2. and the second was due to loss in porosity and formation of large particles of α-Fe2O3 as observed earlier (Balek and Subrt. and later as six-line ferrihydrite. and iron oxide. In this study.1.nH2O Subsequently.1.2 Thermogravimetry Thermal analysis of the precipitates showed two endothermic peaks in the beginning. This is possible even at low temperature. ferrihydrite transforms itself to different phases of iron oxyhydroxide. and subsequent de-hydroxylation results in products with high surface area. However. and the second one for dehydroxilation taking place between 280-300 oC. 3. as two-line. the route for transformation was dependent on the presence of water during aging. Page 7 of 24 . 3. These are similar to reported findings in earlier studies (Norihito et al. application of microwave energy during precipitation of iron oxy-hydroxides.1. 3. 3. as dehydroxylation takes place.

The presence of γ-Fe2O3 was also confirmed from DTA plot. On heating.833 (OH)0.2 oC. more crystalline iron oxyhydroxide crystals were formed. corresponding to Fe1. with the minimum crystallite size of 70.3. and Wolska and Schwetmann. with sharp diffraction peaks of strong intensity.2.251 corresponding to (110) plane. In this study. formed at low temperatures. Several studies have shown that Fe1.5 .5O2. where its transformation to α-Fe2O3 occurs at 539. 2008.5O2. subsequent in their place. Hu et al.93 m2/g.833 (OH)0.6nm. Figure 6a is TEM image of N602 sample prepared by normal method.5 was dark brown. and to poorly crystalline α-Fe2O3 (JCPDS file 33-0664) on the seventh day. 2002).5O2. it easily transforms to -Fe2O3.833(OH)0.5 (JCPDS file 76-0182). In this study.6nm on (024) plane. Page 8 of 24 . and 97. Subsequently. similar to -FeOOH .5 is non-stoichiometric -Fe2O3 (Ahmad et al. we observed that Fe1.833(OH)0. It shows large and uneven α-Fe2O3 grains. 2009. and in contrast to red colour of -Fe2O3. by their early appearance. amorphous two-line iron oxyhydroxide was formed similar to earlier reported observations (Loan et al.833(OH)0. Fe1. the precipitate transformed to γ-Fe2O3 (JCPDS file 39-1346) on the fifth day. This oxyhydroxide phase has FWHM value of 0.5O2.1 Normal method (sample N602) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Figure 2 shows the XRD patterns of samples prepared using normal method. As aging continued.5 peaks were distinguished from those of -Fe2O3. It illustrates that after ageing in a water bath at 60 oC for one day.5O2. These α-Fe2O3 particles have small surface area of 16.77% degree of crystallinity The Average crystallite size was estimated to be 91. and aged for seven days. 1985) that temperatures >40oC promote formation of crystallites of >10 nm and as low as 9 m2/g surface area. and appearance of -Fe2O3 colour of Fe1. The second distinction was the disappearance. 1989). This is in good agreement with earlier observations (Schwertmann et al.

Then it slowly transformed to crystalline Fe1. The presence of amorphous.3.833(OH)0. With continued aging to 10 hours. The crystallinity of the precipitate at this stage was 98. 3. after 12 hrs of aging under microwave. crystalline phase appeared after 8 hours of aging (Figure 4) Fe1. 0.5O2. Earlier studies have shown (Wohlfarth. But the crystallite size was reduced to 71.3 Aging of precipitate with added water (sample MW610) In this sample. 2007). during microwave radiation.5 m2/g (Table 2). MW610 brought out the role of excess water. without going through metastable-Fe2O3 phase.5 and a small number of goethite peaks appeared.2. FWHM of 0. This study showed that excess water and microwave radiation accelerated phase transformation from an Page 9 of 24 . (Du.73%. The presence of lepidocrocite was not detected in diffractogram. and FWHM of (110) plane was 0. perhaps because of its low concentration.5nm. which also has a role in the oxidation of magnetite to -Fe2O3. as observed earlier.833 (OH) 0.23%. The effect of microwave aging was in accelerating the formation of crystalline phase. The amorphous nature of M610. with crystallinity up to 98.5 m2/ g. This transformation occurred.5 after ten hours.33%. which promoted formation of better crystalline phases.110.1 nm. The XRD pattern after 12 hours of aging shows strong and sharp α-Fe2O3 peaks with good crystallinity of 99. was also supported by TEM (Figure 6b) and large BET surface area of 375. 1987) that iron oxides have great affinity for water. two-line iron oxyhydroxide was observed till 8 hours of aging.149 for (110) plane and estimated crystallite size of 99.147 FWHM of (110) plane.2. and surface area of 253.98%. The TEM image of MW610 at 12 hours of aging under microwave (Figure 6c) shows predominant presence of olive-like α-Fe2O3 with average diameter of ~100 nm or less.2 Microwave aging of precipitate (sample M610) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Figure 3 shows XRD patterns of M610 after aging for 4-12 hours at 60oC. and a few hexagonal lepidocrocite . more intense and stronger diffraction peaks appeared with crystallinity up to 98.5O2.

88% crystallinity.9 nm after 12 hours. and MW610.g. to crystalline -Fe2O3. With increasing aging time.2. the sample showed 96. microwave radiation during aging accelerates the formation of crystalline phase. In the absence of microwave heating. 58. and finally to α-Fe2O3 . Low temperature aging of iron hydroxide at 60 oC first transformed it to two-line ferrihydrite.9 nm after 10 hours. This showed that precipitation and aging process of iron oxyhydroxides under microwave radiation can produce highly crystalline nano particles of α-Fe2O3.5O2. and 60. shows the presence of strong diffraction peaks after microwave aging for 4 hours -far ahead of the samples generated in all the previous three techniques. Conclusions The following may be concluded from the four different methods of aging of iron oxyhydroxides.17 FWHM of (110) plane.5. 0. and then to Fe1. the kinetics of transformation is additionally increased. It shows olive-like α-Fe2O3 nanoparticles with average size of approximately 100nm. and average crystallite size of 57. as shown in Figure 4. 4.4 Microwave radiation during precipitation. the transformation was slow and promotes formation of Page 10 of 24 . Table 1 summarises the experimental conditions of all the samples studied in this work. the TEM image of MM610. The observation from diffractograms is also supported by Figure 6d. After 8 hours.1 nm. Figure 5.almost amorphous precipitate.833(OH)0. If precipitation as well as aging is carried out under microwave. The same 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 behaviour was also observed for MM610. used in this study i. 3. and aging of precipitate with added water (sample MM610) As observed for samples M610. larger crystallites were formed e.

and (c) the stability of phases.5O2. This low temperature technique can be applied to modify (a) the rheology of slurry.2010285 and No. The α-Fe2O3 particles produced under microwave have about 350 m2/g surface area.833(OH)0. and its subsequent transformation to α-Fe2O3 in 6-8 hours. This study showed that microwave mediated aging can produce α-Fe2O3 particles of less than 100 nm size. (b) the adsorption properties. iii. iv. and crystallites of 60 nm. as measured from TEM image. in presence of excess water. The role of microwave is mostly rapid heating. helps the initial formation of crystalline non-stoichiometric Fe1. 21061007) and The Analytical Testing Foundation of Kunming University of Science and Technology (Grant No. much larger than that obtained during conventional high temperature calcination of hydroxide (Schwertmann et al. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 ii. Acknowledgements The authors would like to express their gratitude for the financial support of National Nature Sciences Foundation of China (Grant No. Earlier studies claim that the non-thermal microwave energy is too small to affect the chemical bond. because it is carried out below the boiling point of water.2011194).5.γ-Fe2O3 as an intermediate phase. Page 11 of 24 . as measured from XRD patterns. and thereby accelerating the dehydroxylation process. This has a distinct advantage. 1985). Aging under microwave.

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Zeitschrift für Kristallographie . Tu Jianhua. North Holland Publishing Co. 1989. Peng Jinhui. Research Progress in Synthesis Methods of Aluminium Nitride Powders. Preparation and mechanism of 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 formation of acicular goethite–magnetite particles by decomposition of ferric and ferrous salts in aqueous solution using microwave radiation. E. Materials Research Bulletin... 223-237.P.. Zhang Libo.Crystalline Materials: 189(3-4). 33(1). E. Nonstoichiometric structures during dehydroxylation of goethite.. Whittaker. 1998. Schwertmann. Holland Wolska. Materials Review.G. Amsterdam. 11(19). Xiangyuan Ma. Ferromagnetic Materials: A Handbook on the Properties of Magnetically Ordered Substances. Xia Hongying. . Zhang Shimin. 420-421. 1987. 314-317 Page 14 of 24 . 1571-1579 Wohlfarth. Song. L. U. 2005. G.. A..Wang. Volume 2. Harrison..

List of figures 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65       Figure 1: Photograph of the microwave furnace used. (c) MW610. Figure 2: Comparison of XRD patterns of sample N602 Figure 3: Comparison of XRD patterns of sample M610 Figure 4: Comparison of XRD patterns of sample MW610 Figure 5: Comparison of XRD patterns of sample MM610 Figure 6: TEM images of (a) N602. (d) MM610 corresponding to diffractograms in Figures 2-5.(b) M610. Page 15 of 24 .

List of tables 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65   Table 1: Parameters of samples prepared by various methods. Table 2: Surface area. pore volume. and pore size of different samples as determined by BET technique. Page 16 of 24 .

5O2.5O2.5 α-Fe2O3 60 oC M610 25 °C 24h room condition 25 °C 24h room condition >100.833 (OH) 0.0 60 oC MW610 Fe1.833 (OH) 0. for 10h under Microwave radiation Filtered cake + 100 mL water.833 (OH) 0. aged at 60 oC. for 7 days on steam bath Filtered cake aged at 60 oC.Table 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Sample number Preparation condition Aging condition Major phases Average Crystallite size (nm) 91.5O2.5 -Fe2O3 α-Fe2O3 α-FeOOH Fe1.9 60 oC Page 17 of 24 . aged at 60 oC.5 α-Fe2O3 58.833 (OH) 0. for 10h under Microwave radiation Fe1. for 10h under Microwave radiation Filtered cake + 100 mL water.6 Dehydroxylation temperature N602 ° 25 C 24h room condition Filtered cake aged at 60 oC.5 α-Fe2O3 α-FeOOH 71.5O2.7 60 oC MM610 25 °C 12h Microwave radiation Fe1.

40 Pore volume (cc/g) 0.143 0.273 0.254 Average width of pore (nm) 2.670 34.93 375.6472 29.678 Page 18 of 24 .5 253.174 0.5 355.130 34.Table 2 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Samples Surface area (m2/g) N602 M610 MW610 MM610 16.

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Figure 1 Page 19 of 24 .

Figure 2 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Page 20 of 24 .

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Figure 3 Page 21 of 24 .

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Figure 4 Page 22 of 24 .

Figure 5 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Page 23 of 24 .

Figure 6 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Page 24 of 24 .