Dear Mr.

akbar: We are willing to consider publishing the conference-related manuscript listed below, which you submitted to Transactions on Magnetics - Conferences in conjunction with the ICSSP 2013, pending your successful completion of the revisions which our reviewers feel the work requires. Their comments and suggestions are below and/or in separate files which may be read by going into the "Manuscripts with Decisions" queue in your Author Center and clicking the "view decision letter" link for this paper. Please submit the revised manuscript by going to the "Manuscripts with Decisions" queue of your Author Center on our Manuscript Central Web site, http://mc.manuscriptcentral.com/magconf-ieee. (You are receiving this message because you are listed as the corresponding author of the paper; if one of your coauthors actually performed the initial submission and appears as submitting author, then the paper will be in his or her account, not yours.) Then click the "create a revision" link to generate the draft revision. Once the revision is generated, the first step is to respond to the reviewers' comments. Scroll down to Step 1, and enter your response in the designated area. Then click "Save and Continue", and complete the other steps for submission, Once we receive your revised version, it may be sent again to reviewers, who may recommend further changes before a final decision on publication is reached. Please submit your revision within one week. Because of the limited amount of time for the conference review process, extensions cannot be granted. If we do not hear from you we will have to assume that you have decided to withdraw your paper, and the option to submit the revision will be removed from your Author Center. Please feel free to get in touch with me if you have any questions about the revision or how to submit your edited version. I will look forward to receiving your completed work. Sincerely, Dan Wei Editor Transactions on Magnetics - Conferences Manuscript Title: Development of Mo containing Fe-Cr-Co Permanent Magnets by Modified Single Step Thermo-magnetic Treatment ID: MAGCON-13-12-1329 Paper Type: ICSSP 2013 Conference Paper Number: HS-33 Reviewers' comments to author, if any (please also check your Author Center for other files): Reviewer: 1 Comments to the Author In this paper, it is shown that iHc of over 1000 Oe is obtained for Fe-Cr-Co system alloy by the thermomagnetic treatment. It seems that this method has advantage of reduction of manufacturing time. However, leaps between experimental results and conclusion obtained based on results are occasionally seen through this paper. Especially, I'm feeling inadequacy about the results of XRD and interpretation of that. And I think you need many modifications in spelling, grammar, or usage. Please check the attached file. 1

Reviewer: 2 Comments to the Author This paper tried to develop a new method to produce Fe-Cr-Co-Mo magnet. Some of the results are valuable to the research of the hard magnets without rare-earth. However, there are several points need to be considered before it can be accepted for publication. 1. There are many typos and format errors, which should be avoided. For example in page 2, left column, first paragraph, last sentence is not understandable. 2. From Fig. 2, it is obvious that peak position shifts to a higher angle. There is no explanation about this phenomenon. 3. There are no hysteresis loops in the manuscript, which is hard to judge the magnetic properties of the materials 4. It is noticed that the BHmax of the anisotropic magnet is lower than that of the isotropic, which it is abnormal for the magnetic materials. Some justification is required. 5. The coercivity of this kind of the magnets is related to the shape anisotropy. It is desirable to provide some data about the length to diameter ratio dependent magnetic properties. The heat treatment effect on the shape and phases could give more insight on how to improve the magnetic properties of these compounds.

In this paper, it is shown that iHc of over 1000 Oe is obtained for Fe-Cr-Co system alloy by the thermo-magnetic treatment. It seems that this method has advantage for reduction of manufacturing time. However, leaps between experimental results and conclusion obtained based on results are occasionally seen through this paper. Especially, I'm feeling inadequacy about the results of XRD and interpretation of that. And I think you need many modifications in spelling, grammar, or usage. I recommend you to undergo the English proofreading by the native speaker. Please confirm the below comments. 1. I recommend to undergo the English proofreading by the native speaker. I think you need many modifications in spelling, grammar, or usage. For example, #Page 1 left paragraph line 46 samplessubjected samples subjected #You use five hours, in page 1 line 14 and 5 hours in page 1 line 35 I think you should standardize it. #Page 1 right paragraph line 39 I think you should not be use & and use the and. #Page 2 left paragraph line 17 Fig. 1a Fig. 1 (a) #Page 2 left paragraph line 23 You use good sometimes in this article. I think good should be avoid to use in scientific papers as far as possible. #Page 2 right paragraph line 17 I think you should standardize alpha and . 2. Page 2 left paragraph line 15 You say single phase structure (bcc-phase) was observed by Optical microscopic.

I think it is difficult to recognize that by optical microscopic. I think you should explain the result of XRD (3.2 X-ray diffraction analysis) first. 3. Page 2 left paragraph, F1g. 1 (b) There are no mentions about this figure. Distinct difference is observed between Fig. 1(a) and Fig. 1(b). Grain size of Fig.1 (b) is obviously larger than that of of Fig.1 (a). (you should uniform the scale of these figures) This difference in grain size will affect the result of XRD. 4. Page 2 right paragraph line 2 I think these samples are samples after TMT at 635 for 5 hours. But, you should explain the condition of samples of Fig. 1(c) and (d), water quench (Fig. 1(a)) or after TMT at 635 for 5 hours (Fig. 1 (b)). 5. Page 2 right paragraph line 5 You say, ~ rod like a1 phase (FeCo rich) is ~ How did you confirm FeCo rich ? you should show the results of SEM-EDX or something. 6. Page 2 right paragraph, F1g. 2 You put the value of degree in these figures. I think you should show the put the plane index of these samples. The amplitude of back ground of Fig. 2 (b) is obviously larger than that of Fig. 2 (a). Is number of counts of Fig. 2(b) enough? 7. Page 3 left paragraph, line 3 I have a question about this discussion. As mentioned above, it can see that grain size of sample after TMT at 635 for 5 hours is very large (Fig. 1 (b)). if the X-ray irradiated area size was about 1cm2, it is estimated that the number of grains measured by XRD is under 10 at most from Fig. 1 (b). I think it is hard to discuss about the width of peak and to apply the Scherrers formula. 8. Page 3 right paragraph, line 59 Sample 7. If you use the sample number, you must explain about it.

Development of Mo containing Fe-Cr-Co Permanent Magnets by Modified Single Step Thermo-magnetic Treatment
Shakeel Akbar1, a, M. A. Aleem, M. S. Awan1, b,Zubair Ahmad1, and Muhammmad Farooque1
1

IICS, P.O Box 1398, Rawalpindi, Pakistan. PIEAS, P. O.

sam_qau@yahoo.com, adeel713@gmail.com, bsss_awan@yahoo.com

Abstract Present study is focused on a new approach which aimed to ease up the development of Fe-Cr-Co-Mo permanent magnets. Tri arc melting technique under inert atmosphere of Argon was used for the preparation(Synthesis/development) of Fe-Cr-Co-Mo alloy. Solution treatment was done at a temperature of 1250 oC for 5 hours followed by water quenching and then samples were subjected to thermo-magnetic treatment (TMT) at 630 oC at predetermined cooling rates. The influence of TMT and cooling rates on the final magnetic properties of the alloy were investigated. Microstructural, XRD and magnetic characterization were carried out. It was observed cooling rates and TMT temperature both affect the magnetic properties of material. Spinodal structure was observed at 50 k magnification of SEM: rod like 1 phase (FeCo rich) is embedded in the matrix of 2 phase (Cr rich). The average length of the 1 rod like particles is 150 + 30 nm and the diameter is 30 + 10 nm(may be removed if evidence not present). Resultant magnetic properties are as 903 Oe (Hc), 10.4 kG (Br), 4.3 MGOe (BHmax) with two steps aging process and 990 Oe (Hc), 8.8 kG (Br), 3.1 MGOe (BHmax) with continuous cooling up to 540 oC. Current method provides a quick and low cost manufacturing route for the Fe-Cr-Co-Mo permanent magnets with magnetic properties comparable to that of AlNiCo with added advantage of having high ductility. Keywords: Permanent magnets; Spinodal structure; Thermo-magnetic treatment compared to 50-60 hours with a little compromise on magnetic properties. 2. Experimental Procedures In this work casting route was adopted and tri arc melting furnace was used for the production of proto type samples using high purity (99.9%) elements. Chemical composition of alloy was analyzed by EDX technique. Traces of Carbon and Sulfur were identified using CS analyzer after calibrating with standard samples. The average chemical composition of the studied alloy was Fe-25Co-29.5Cr-3.33Mo-0.0075S0.007C (wt %). Cube samples of 10 mm3 were used in this study. These samples were solution treated at 1250 o C for 5 hours and water quenched from 1250 oC to room temperature. The samples were then subjected to the thermo-magnetic treatment (TMT) in temperature range of 625-645oC for 30 minutes. Three different cooling rates 0.5, 1 and 2 oC per minute were selected for the cooling of sample from TMT temperature to 500 o C. Magnetic field (2.5 kOe) was applied in the TMT temperature range and switched off during cooling down to the temperature 500 oC and then the samples were air cooled. This treatment was done in an indigenously developed magnetic field annealing

1. Introduction Fe-Cr-Co alloys fall in semi hard magnetic materials regime. In addition to magnetic properties their prime features are machinability,high Curie temperature (850C); working temperature up to 500C and remanence comparable to other magnetic alloys e.g., Nd-Fe-B [1], [2]. Both isotropic and anisotropic magnets can be produced with Fe-Cr-Co alloys. The source of magnetism in this alloy is well explained and conventional production cycles are discussed in [3]-[6]. Hot rolling / cold rolling were performed prior to thermo-magnetic treatment (TMT) apply to enhance the shape anisotropy of the alloy for improved magnetic characteristics [7]. A four steps heat treatment applied for secondary re-crystallization (HTSR) process in order to enhance the magnetic properties [8]. A few researchers also worked on the gradient microstructure subjected to deformation by tension and torsion at >700oC [9]-[10]. Objective of this work was an attempt to avoid complicated hot rolling/cold rolling or HTSR processes. By the single step heat treatment cycle used in this study, processing time reduced to just 08 hours as

system with the magnetic field intensity of 2.5 kOe and temperature accuracy of + 2 oC. Phase identification was carried out using optical microscope and XRD with CoK (1.7902 ) radiation. The samples were scanned for 2 range of 45 to 105. Microstructural study was carried out using Optical Microscope (OM) and Scanning Electron Microscope (SEM) equipped with an Energy Dispersive Spectrometer (EDS). Sample for microscopic studies were prepared by standard metallographic procedure of grinding followed by polishing down to 0.5 m finish using silicon carbide paper and diamond paste. Polished sample were then etched electrolytically in 10 % Chromic acid solution. Magnetic properties were measured by a using Gauss meter and DC Magnetometer. 3. Results and Discussion Effect of TMT and cooling rate on the magnetic properties of Fe-25Co-29.5Cr-0.53Ti-3.33Mo0.015C-0.007S wt % alloy was investigated. 3.1 Microstructural Studies Optical microstructures of solution treated and fully treated samples are shown in Fig 1(a) and (b) respectively. There is no evidence of any desirable phase on the grain boundaries and within the grain. However the presence of single phase is confirmed by XRD data. Optical microscopic studies of solution treated samples at 1250 oC have only single phase structure (bcc -phase) as shown in Fig. 1(a). Homogeneity of the material was determined by SEM elemental image mapping which is good. If the samples were furnace cooled/ air cooled: they have undesirable tetragonal sigma () and fcc gamma () phases at the grain boundaries and within the grains. In order to achieve desirable magnetic and mechanical properties material should be free of these unwanted phases. Growth of sigma phase is more likely in the upper limit

of the Spinodal decomposition temperature as 670 oC or above. This observation has coincidence with the previous reported result by F. Vodopivec et al [11]. Fully processed samples by above said treatment (TMT is 630-635oC) composed of single phase structure and there is no evidence of any of the harmful phase like or . SEM at high magnification (50,000) revealed spinodal phases as shown in Fig. 1(c) and (d). Images were captured from two different directions; parallel to the applied magnetic field and perpendicular to the field. The rod like particles which are embedded in black matrix are expected as Fe-Co rich 1 regions while the matrix is expected to have Cr rich 2 phase. [4] The anisotropic effect of the magnetic field on the grain growth of 1 particles was pronounced as evident in Fig. 1 (d). The average length of the 1 rod like particles is 150 + 30 nm and the diameter is 30 + 10 nm. The length to diameter ratio (~5:1) is expected to play a vital role in the evolution of anisotropy leading to improved magnetic properties. 3.2 X-ray Diffraction Analysis XRD pattern of solution treated samples shows three peaks at 2 = 52.1, 76.4 and 99, all corresponding to bcc (-phase), while there is no evidence of the presence of fcc (-phase) or any other phase. Therefore, the above mentioned solution treatment procedure was found suitable for producing single -phase material.

Fig. 2a & b confirm the existence of bcc structure only. It also observed that furnace cooled samples after 1250oC for 5 hours and as cast sample

(a)

(b)

(c)

(d)

H//

Fig. 1: Microstructure of solution treated sample at 1250oC for 5 hours (a) water quench (b) after TMT at 635oC for 30minutes (free of undesirable phases like sigma and gamma) (c) field perpendicular view (d) field parallel view.

Fig. 2: XRD patterns (a) water quenched sample after solution treatment at 1250 oC for 5 hours (b) after TMT at 630 oC for 30 minutes (free of 5 undesirable gamma and sigma phases).

have undesirable phases like gamma and sigma phases (XRD patterns are not shown). The peak broading in the initial and final XRD data is due to the grain size reduction of alpha phase particles inside the matrix. Whereas, the shoulder of the peak (110) in the Fig. 2b is the sign of the spinodal decomposition of the material. 3.3 Magnetic properties analysis From XRD patterns as shown in Fig. 2, it was observed that peak broadening (FWHM) of solution treated sample increases after the TMT. Mean size of grain, as measured using Scherrers formula [1 2], was 41nm after solution treatment while after TMT it reduced to 17nm. The grain size 30 + 10nm observed by SEM at 50k magnification in direction perpendicular to applied field shows good agreement with the XRD results. This reduction in size of the 1 phase is due to elongation of 1 particles by TMT, their diametric size should be reduced which is confirmed by XRD patterns taken perpendicular to the applied field. From the SEM results it is gathered that the number density and volume fraction of the 1 particles is considerably satisfactory. Among magnetic properties, the saturation magnetization Ms, is independent of particle size, but the coercivity Hc shows a significant dependence. The major factor of coercivity in Fe-Cr-Co is due to the size of the magnetic particles (1) and the rotation of the magnetic moments of the magnetic phase 1 [6]. The appropriate 1 particle size will result in a high Hc value in our case is most probably due to reduction in size at different stages i.e. homogenized and fully processed. This small size (30nm) at the fully processed stage leads to high coercivity (>900 Oe). Table 1: Optimization of TMT for 30 minutes with cooling rate 2 oC/minute. Flux Br iHc BHmax TMT (oC) (G) (kG) (Oe) (MGOe) 625 215 9.2 520 1.7 630 630 10.6 810 3.6 635 520 8.1 900 2.8 640 400 8.6 815 2.0 645 345 8.0 600 1.4

and their shape. Magnetic properties are evolved in FeCr-Co alloys due to spinodal decomposition during TMT. Upon the decomposition, molybdenum concentrates in paramagnetic phase 2 and causes lattice parameter difference between 1 and 2phase, thus affecting the morphology of the precipitated phases [1],[4],[5]. A heat treatment cycle having longer TMT duration results in coarsening the particles and in turn decreases Hc [7]. Table 1-3 gives relation between the magnetic properties and TMT temperature along with cooling rate. Initial size of 1 particle and its shape is very much influenced by even minor change in the TMT temperature and cooling rate as it is presented in table 1&2 and observed by others researchers [13]. So it is very critical to have precise temperatures inside

the furnace. In order to comply with precision an indigenously developed furnace with temprature precision up to +2 oC was used. Hc and Br have maximum values in the range 630-635oC. For
isotropic magnets many of the samples were processed in the absence of applied magnetic field and the average of their results is shown in Table 2. As the TMT temperature was optimized and the effect of cooling was observed, the heat treatment cycle was modified. In modified heat treatment cycle samples were cooled to 600 oC at cooling rate as low as 0.5 oC / minute and then the samples were subjected to the two step aging process. The magnetic measurements were carried out after each stage and shown in Table 3. Coercivity of the material decreased moderately from 950 Oe to 900 Oe during the step aging process while the remanence and energy product of the material increased from 9.0 kG to 10.4 kG. The possible reason for this phenomenon is the growth of the alpha1 particles by aging process. As a result energy product of the material was enhanced contributing to the magnetic hardening. Table 3: Sample were processed by two step aging. Stage Flux Br iHc BHmax (G) (kG) (Oe) (MGOe) 1 600 9.0 950 3.3 2 650 10.1 882 4.1 3 700 10.4 900 4.3 o RT - TMT (30mint stay) cool@ 0.5 C/mint. to 600oC AC (Stage 1) First aging 600/1h- 580/2h (Stage 2) Second aging 570/10min. - 560/2h- 550/2.5h (Stage 3)

Table 2: TMT for 30 minutes o C/minute Flux Br TMT (oC) (G) (kG) 630 550 9.4 635 500 7.6 630 440 8.0 (Isotropic)

with cooling rate 1 iHc (Oe) 1010 1100 880 BHmax (MGOe) 3.4 2.9 2.3

Major factors that influence the magnetic properties are volume fraction of the spinodal decomposition product

4. Conclusions Magnetic properties of alloy having the composition Fe-25Co-29.5Cr-0.53Ti-3.33Mo-0.0075S0.007C (wt %) was optimized by modified two stage aging treatment. Samples solution treated at 1250 oC for 5 hours were free of undesirable phases. TMT temperature was optimized for above mentioned composition and effect of cooling rate was studied. The

optimized TMT temperature was found to lie in between 630-635oC. Slow cooled samples showed better Hc value as compared to the fast cooled. Sample processed by continuous cooling process at TMT 635 oC and cooling rate 1oC/ minute showed coercivity 1100 Oe (table 2). The sample processed by two step aging cycle showed remanence 10.4 kG, and a maximum magnetic energy product 4.3 MGOe (table 3). Acknowledgement Authors would like to thank Muhammad Irfan for XRD, Umar Farooque for the raw material, Naveed Hassan Tahir, Faisal pirandadand Naveed Iqbal for their help in processing.

[10] [11]

[12] [13]

G. Korznikova and A. Korznikov, Materials Science & Engineering A 503 (2009) pp 99. F.Vodopivce, J. Zvokelj, B. Breskvar, D.Gnidovec, A. Rodic and M. Torkar, Microstructure and Ductility of Fe28Cr16Co Alloy with Addition of Si, Mo, Ti and Al Z. Metallkde, Mag.85 No.3(1994), pp 207-212. B.D. Cullity, Introduction to Magnetic Materials, Addison Wesley, Ch. 11, 1972. S. Sugimoto, J. Honda, Y. Ohtani, M. Okada and M. Homma, Improvements of the Magnetic Properties of Equiaxed Fe-Cr-Co-Mo Hard magnets by Two step Thermo-magnetic Treatment IEEE Transactions on Magnetic, Mag. 23 No. 5 (1987) pp 3193-3195.

References [1] H.J. Fastenau, E.J. Loenen, JMMM, Application of rare earth permanent magnets, Journal of Magnetism and Magnetic Materials, 1570158 (1996) pp 1-6. [2] M.E. McHenry, M.A. Willard, David E. Lauglin, Amorphous and nano-crystalline materials for applications as soft magnets Progress in Materials Science, 44 (1999) pp 291-433. [3] S. Akbar, Z. Ahmad and M. Farooque, Development of Fe-Cr-Co Permanent Magnets by Single Step Thermo-magnetic Treatment Key Engineering Materials Vol. 442 (2010) pp 236-241. [4] Z. Ahmad, S. Akbar, M. Farooque, A. ul Haq and Mi Yan, Synthesis and magnetic properties of Nb-doped Al-Ni-Co-Ti-Cu-Fe Permanent magnets Philosophical Magazine Letters, Vol.91, No.3 (2011) pp 173181. [5] Z. Ahmad, A. ul Haq, S.W. Husain, A. Ali, T. Abbas, Influence of Ti Content on Magnetic and Microstructural properties of Fe-28Cr-15Co3.5Mo Permanent Magnets JMMM 257(2003) pp 397-402. [6] S. Jin, G.Y. Chin and B.C. Wonsiewicz, A Low Co Ternary Cr-Co-Fe Alloy for Telephone Receiver Magnet use IEEE Transaction on Magnetics, Mag 16 No. 1 (1980) pp 139-146. [7] G.V. Sidorova, V.P. Korneev, I.M. Milyaev, L.V. Kovalenko and S.P. Efimenko, Structural Changes in Fe-Cr-Co Alloy in the Initial Stage of the Formation of Highly Coercive State Metalloy, 6(1997) pp 107-110. [8] S. Sugimoto, H. Satoh, M. Okada and M. Homma, Evolution Process of <100> Texture in Fe-Cr-Co-Mo Permanent Magnets Materials Transactions JIM, mag. 32 No.6 (1991) pp 557561. [9] A. Korneva, G. Korznikova and A. Korznikov, Gradient Microstructure in FeCr30Co8 Hard Magnetic Alloy Subjected to Tension Combined with Torsion Rev. Adv. Mater. Sci. 31 (2012) pp 36-39.