Full Papers Thailand Metallurgy Conference

FullPapers
The3rdThailandMetallurgyConference (TMETC3)
MetallurgicalResearchforThailandDevelopment 2627October2009 CenturyParkHotel,Bangkok,Thailand

Organizedby
DepartmentofMaterialsEngineering,KasetsartUniversity IronandSteelInstituteofThailand NationalMetalandMaterialsTechnologyCenter

Sponsoredby
SahaviriyaSteelIndustriesPublicCo.,Ltd ThaiParkerizingCo.,Ltd BoonRawdBreweryCo.,Ltd. ThaiNipponSteelEngineering&ConstructionCorp.,Ltd. AdvancePinnacleTechnologiesPteLtd. DKSHLtd. CouncilofEngineers,Thailand
OrganizingCommittees
ConferenceChairman
Asst.Prof.WisitLocharoenrat DepartmentofMaterialsEngineering,KasetsartUniversity
AdvisoryCommittee
Mr.Wikrom Vajragupta IronandSteelInstituteofThailand Assoc.Prof.Dr.WeerasakUdomkichdacha NationalMetalandMaterialsTechnologyCenter Assoc.Prof.Dr.ParitudBhandhubanyong NationalScienceandTechnologyDevelopmentAgency Assoc.Prof.Dr.ChatchaiSomsiri ThainoxStainlessPcl.
TechnicalCommittee
FacultyofEngineering,KasetsartUniversity Asst.Prof.WisitLocharoenrat Dr.AmpikaBansiddhi Dr.AphichartRodchanarowan Dr.Ing.PatiphanJuijerm NationalMetalandMaterialsTechnologyCenter Dr.EkkarutViyanit Dr.RuangdajTongsri Dr.JulathepKajornchaiyakul Dr.KritsadaPrapakorn Dr.ParinyaChakartnarodom Dr.RatchateeTechapiesancharoenkij Mr.ThanawatMeesak
FacultyofEngineering,ChulalongkornUniversity Assoc.Prof.Dr.GobboonLothongkum Assoc.Prof.Dr.PrasonkSricharoenchai Asso.Prof.CharkornJarupisitthorn Asst.Dr.SawaiDanchaivijit Asst.Prof.Dr.EkasitNisaratanaporn Mr.SuvanchaiPongsugitwat MetallurgyandMaterialsScienceResearchInstitute,ChulalongkornUniversity Ms.KanokwanSaengkiettiyut Dr.NutthitaChuankrerkkul FacultyofEngineering,KingMongkutsUniversityofTechnologyThonburi Assoc.Prof.Dr.ChaowalitLimmaneevichitr Assoc.Prof.DrBovornchokPoopat Asst.Prof.DrSombunCharoeuvilaisiri School of Energy, Environment and Materials, King Mongkuts University of Technology Thonburi Asst.Prof.Dr.SiripornRojananan Dr.PreechaTermsuksawad FacultyofEngineering,KingMongkut'sUniversityofTechnologyNorthBangkok Asst.Prof.Dr.SomrerkChandraAmbhorn Asst.Prof.Dr.WitthayaEidhed Dr.NattapongSornsuwit Dr.TippabanPalathai Dr.PongsakTuengsook Dr.Ing.PaiboonChoungthong Mr.NoppadolKumanuvong Dr.YuttanantBoonyongmaneerat Dr.TachaiLuangvaranunt Dr.SeksakAsavavisithchai Asst.Prof.Dr.PatamaVisuttipitukul Dr.PanyawatWangyao Dr.BoonratLohwongwatana
School of Metallurgical Engineering, Institute of Engineering, Suranaree University of Technology Dr.NarongAkkarapattanagoon Dr.UsaneeKitkamthorn FacultyofScience,ChiangmaiUniversity Assoc.Prof.Dr.TorraninChairuangsri FacultyofEngineering,PrinceofSongklaUniversity Asst.Prof.Dr.ThawatchaiPlookphol Asst.Prof.Dr.JessadaWannasin Dr.RattanaBorisuttikul Dr.SakhobKumkoa
The3rdThailandMetallurgyConference
Effect of welding processes on the microstructure and hardness properties of weld metal on low alloy steel AISI 4340
S. Limna, P. Muangjunburee
Department of Mining and Materials Engineering, Faculty of Engineering, Prince of Songkla University, Hatyai, Songkla, 90112 Thailand Tel: +6674 287323 Fax: +6674 212897 Email: b_rainning@hotmail.com
Abstract In this work, the microstructure and hardness properties of weld metal on low alloy steel AISI 4340 have been investigated using shielded metal arc welding, metal active gas welding and flux cored arc welding processes which the composition of filler wire nearly the same alloying elements. The samples were mutipass welding. The microstructure and hardness properties in weld metal were investigated by using optical microscope and micro hardness tester. The microstructure of weld metal all three processes consisted of acicular ferrite, grain boundary ferrite, polygonal ferrite and sideplate ferrite. However, the microstructure of weld metal fabricated using flux cored arc welding process indicates higher volume fraction of acicular ferrite than metal active gas welding and shielded metal arc welding process. The results have revealed that the hardness of the weld metal fabricated using flux cored arc welding process is greater than the weld metal fabricated using shielded metal arc welding and metal active gas welding process. Keywords : AISI 4340; Welding; Acicular ferrite; Polygonal ferrite
1. Introduction Low alloy steel AISI 4340 are used in heavy duties engineering application for a long time. This is a widely used low alloy steel that offers an advantageous due to high hardness, high strength and excellent toughness [1-3]. As the machine part-members age, degenerate and may fail in service or be declared unfit for further service on the basis of inspection and remaining life assessments. Therefore, the machine part-members are repaired by welding processes. However, welding can change the microstructure. Thus mechanical properties were degraded in weld metal and heat affected zone (HAZ). Shielded metal arc welding (SMAW), Metal Active Gas welding (MAG) and Flux cored arc welding (FCAW) process
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are widely used in welding repair of machine part-members [4,5]. MAG and FCAW are a semi or fully automatic arc welding process in which the electrode is continuously fed to the weld area. Solid wire used in MAG but FCAW used flux cord wire that has the flux material in the core of the tube [4]. On the other hand, SMAW is a manual process. Automatic welding processes are favored over manual processes for the fabrication of welded joints for number of reasons. Among these are increasing of productivity, lower cost and a better control of geometry. However, FCAW process has became more popular due to higher deposition rate and a better weld quality as compared to SMAW process [5]. This paper presents an investigation of microstructure and hardness of weld and base metal change after welding by SMAW, MAG and FCAW processes.
2. Experimental The base metal used in this investigation was the commercial AISI 4340 steel. Single bevel butt joints were prepared to fabricate the weld. The samples were multi-pass welded by Shielded Metal arc welding (SMAW), Metal Active Gas arc welding (MAG) and Flux cored wire arc welding (FCAW). Electrodes and process parameters used to fabricate the weld are given in table 1. Welding completion were post-weld heat treatment at 550C for 1 hour. The chemical composition of base metal and weld metal is shown in table 2. Cross section samples were cut from the all weld samples. The samples were ground surface until 1200 grits. After that, samples were polished to a 1 alumina finish. The weld metal microstructure was revealed by etching with a freshly prepared 2% natal solution. The microstructure analysis of the weld metals were studied using a light optical microscope. Vickers microhardness testing machine was used to measure the weld metal and base metal.
3. Results Microstructures The main aim of this investigation was to understand the microstructure of welded sample with different processes such as SMAW, MAG and FCAW processes. The typical microstructures of base metal and weld metal are presented in Fig.1. The microstructure feature of the base metal shows tempered bainite (Fig.1a). In general, the microstructures of weld metal obtained from all processes consisted of acicular ferrite, polygonal ferrite and sideplate ferrite. Volume fraction of microstructures is presented in Fig.3. An optical
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microstructures of weld metals fabricated using SMAW, MAG and FCAW processes present predominantly acicular ferrite. However, the microstructure of weld metal fabricated using FCAW process indicates higher volume fraction of acicular ferrite than MAG and SMAW processes.
Table 1 Welding conditions Parameter Electrode Types (AWS) Unit
SMAW E11018-G 4R
MAG H ER110S-G
FCAW E110T5-K4H4
Preheat temperature Electrode baking temperature Mixer gas flow rate Filler diameter Current Voltage Welding speed Heat input
C C for 1 hr.
350 350 4 145 26 160 1.41
350 12 1.2 230 25 300 1.15
350 12 1.2 230 25 300 1.15
l/min mm. A V mm/min KJ/mm
Table 2 Chemical composition of base metal and weld metals Type of materials Base metal SMAW MAG FCAW C 0.39 0.05 0.08 0.05 Mn 0.74 1.5 1.4 1.40 Si 0.19 0.4 0.6 0.005 P 0.024 0.015 S 0.019 0.50 Mo 0.23 0.5 0.4 2.40 Ni 1.72 2.0 2.5 2.4 Cr 0.8 0.4 0.30 0.50
Hardness Vickers hardness testing machine was used to measure the weld metal and the base metal hardness and the values are presented in Fig.2. From this figure, the hardness distribution of the welds cross section was clearly found to be different among process. The hardness of the base metal is approximate 290 HV. Weld metals fabricated using SMAW, MAG and FCAW processes exhibit 250, 230 and 275 HV, respectively. The hardness value of samples fabricated by FCAW revealed higher hardness in the area of weld metal than samples fabricated by MAG and FCAW processes.
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Fig. 1. Optical microstructures of base metal and weld metal: (a) Base metal; (b) SMAW; (c) MAG; (d) FCAW
Fig. 2. Vickers hardness distribution of base metal (left), weld metal (middle) and base metal (right) of the samples were fabricated by SMAW, MAG and FCAW
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Fig.3. Volume fraction of microstructures in different processes.
4. Discussion It is a common practice to correlate the various weld metal properties with heat input. The difference in the ferrite morphology in low alloy steel welds is due to the difference in heat input. The formation of acicular ferrite is controlled by weld heat input. Thus if the heat input is higher the content of the acicular ferrite will be very less and vice versa. On the other hand higher heat input will enhance the formation of coarse pro-eutectoid ferrite or polygonal ferrite in the weld metal region. Weld cooling rate plays the decisive role in determining weld microstructure in high strength steels. The general effect of increasing the cooling rate is to lower transformation temperatures. When cooled at sufficiently low rates, the microstructure predominantly tends to become polygonal ferrite. In the present investigation, heat input of 1.41 KJ/mm. was fabricated by SMAW and 1.15 KJ/mm. was fabricated by MAG and FCAW. The microstructure of the weld metal region consisted of acicular ferrite, grain boundary ferrite, polygonal ferrite and sideplate ferrite. An acicular ferrite microstructure has the potential of combining high strength and high toughness. Acicular ferrite is formed in the interior of the original austenite grains by direct nucleation from the inclusions resulting in a randomly oriented short ferrite needles with a basket weave features. It has been accepted that polygonal ferrite is bad for weld metal toughness because it offers little resistance to cleavage crack propagation. In addition, the results confirm that the hardness in weld metal fabricated using FCAW process higher than weld metal fabricated using MAG and SMAW process. Therefore, the welding process has a significant in the weld metal microstructure. This has a direct influence in weld metal hardness.
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5.Conclusions The microstructure and hardness properties of weld metal on low alloy steel AISI 4340 fabricated using SMAW, MAG and FCAW processes have been investigated and the conclusions are as follow: 1. The microstructure constituents such as acicular ferrite, polygonal ferrite and sideplate ferrite are influenced by heat input. 2. The hardness of weld metal is significantly depending on microstructure. 3. FCAW process indicates both microstructure and hardness better than SMAW and MAG processes.
6. Acknowledgements The author gratefully acknowledge the financial support from the electric Generating Authority of Thailand (EGAT). Thanks are also to the Department of Mining and Materials Engineering, Prince of Songkla University, Hat- Yai, Thailand for providing equipment and facilities.
7. References [1] P.Muangjunburee. 2007. Improvement of Metallurgical and Mechanical Properties of Welding Surfacing on High Strength Steel AISI 4340 by Various Preheating Temperatures. Proceedings of international Conference the Frontiers of Technolog: 321-324. [2] P.Muangjunburee. 2007. Improvement of metallurgical and Mechanical properties of welding surfacing on high strength steel AISI 4340 by Post-weld heat treatment. The First South-East Asia IIW Congress: 273-277. [3] Woei Shyan Lee and Tzay Tian Su. 1999. Mechanical properties and microstructural features of AISI 4340 high-strength alloy steel under quenched and tempered conditions. Journal of Materials Processing Technology 87: 198-206. [4] G. Magudeeswaran, V. Balasubramanian and G. Madhusdhan Reddy. 2008. Effect of welding processes and consumables on high cycle fatigue life of high strength, quenched and tempered steel joints. Journal of Materials and Design. [5] T.Lant, D.L. Robsinson, B.Spafford and J.Storesund. 2004. Review of weld repair procedures for low alloy steels designed to minimize the risk of future cracking. International Journal of Pressure Vessels and Piping 78: 813-818.
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An investigation of microstructural change of low alloy steel AISI 4150 by Seebeck coefficient
T. Samrana, P. Termsuksawadb*
a
School of Metallurgical Engineering, Institute of Engineering,
Suranaree University of Technology, Nakhon Ratchasima, 30000 Thailand

b
Division of Materials Technology, School of Energy Environment and Materials, King Mongkut's University of Technology Thonburi, Bangkok 10140 Thailand, Tel: 0-2470-8643, Fax: 0-2427-9062 Email: preecha.ter@kmutt.ac.th
Abstract Low alloyed steel, whose hardness can be increased by heat treatment, have been widely used in various applications. After heat treatment, it is normally destructively characterized and tested by many approaches such as microstructure characterization by optical microscope and hardness testing. It is useful to develop a non-destructive method to characterize its properties and microstructures. The Seebeck effect is a phenomenon in which the electrical potential gradient develops due to temperature difference. The magnitude of the Seebeck effect is demonstrated by the Seebeck coefficient, which can be altered by electronic properties or microstructure changes. The materials in this study were cylindrical carbon steels AISI 4150 with diameter of 1.3 cm and length of 3 cm. The specimens were heat-treated at 900 oC for 1 hour, and then cooled to room temperature in furnace and in various mediums: air, oil and water. In addition one of the samples was cooled in salt bath at 350 oC for 1 hour before water cooled. An x-ray diffractometry (XRD) and optical microscopy (OM) were used to characterize their crystal structures and microstructures, respectively. The Seebeck coefficient was measured relative to that of copper. The result indicated that Seebeck coefficient increases with hardness, which is controlled by microstructure. In conclusion, the Seebeck coefficient measurement could be possibly applied to study microstructure of low alloyed steels.
Keywords: Seebeck coefficient, low alloyed steel, heat treatment, XRD, microstructure
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Introduction Low alloy steels are steels with additions of alloying elements such as nickel, chromium and molybdenum. These alloying elements increase hardenability of the steels; as a result, mechanical properties of these steels can be improved by heat treatment. Because these steels possess good mechanical properties, they have been widely used in many applications such as automobile parts, structural steel parts, pipelines, etc. After heat treatment, microstructure of the steels is altered and their mechanical properties such as hardness and strength were improved. Typically, mechanical properties of heat treated steels such as hardness and strength are examined by some destructive tests. Therefore, it is useful to develop a nondestructive technique to predict these properties. One of the candidates is Seebeck coefficient or thermoelectric power measurement which measure amount of induced voltage developed by temperature difference, S AB = lim
V [1]. Seebeck coefficient or thermoelectric power is T 0 T
contributed by two components: diffusion and phonon-drag thermoelectric power. Phonondrag thermoelectric power is very small and can be negligible at room temperature or above. Diffusion thermoelectric power is a function of electrical conductivity and effective mass [2]. Effective mass is defined as curvature of electronic structure at the Fermi level [2]. From this definition, effective mass, m , is calculated by m* =
*
2
d 2E , where dk 2
d 2E and are Planks dk 2
constant, and curvature of electronic structure at Fermi level, respectively. Both electrical conductivity and effective mass are function of microstructure and electronic structure, as a result, Seebeck coefficient depends on these structures as well. It should be noted that sign of Seebeck coefficient depends on types of carriers [3]. If a carrier is an electron, Seebeck coefficient will be negative. In contrast, positive Seebeck coefficient is found when hole is a carrier. The magnitude of Seebeck coefficient depends on effective mass and difficulty of carrier transport. Effects of microstructure of carbon steel on Seebeck coefficient were studied by various research groups [4-7]. Effect of annealing on thermoelectric power of low carbon steel containing 460 ppm aluminium and 74 ppm nitrogen was investigates by Brami et al [4]. In this study, thermoelectric power increased with amounts of AlN and carbon precipitation. For ultra low carbon steel, Seebeck coefficient was found to be decreased with increasing defect concentration or amount of dissolved element in the matrix, and be increased with the
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amount of precipitation [5, 6]. The increasing of Seebeck coefficient due to amount of precipitates was also found in martensitic stainless steel when Caballero et al. studied the effect of carbide precipitation on Seebeck coefficient of heat treated stainless steel [7]. In addition, Caballero et al. indicated that Seebeck coefficient can be increased with grain size of austenite due to decreasing of grain boundary concentration. From literatures; therefore, it is possible to study effect of heat treatment on microstructure and mechanical properties of low alloy steel via Seebeck coefficient. This study aims to investigate this relationship in order to further develop this concept as non-destructive testing for heat treated steel.
Experimental procedure
Low alloy steel grade AISI 4150, whose diameter is 1.3 cm. with the length of 3 cm, was used in this study. The sample composition was analyzed by emission spectroscopy as shown in table 1. From this table, main alloying elements in this steel are chromium and molybdenum, which increases hardenability of the steel. Table 1: composition of sample, analyzed by emission spectroscopy (wt.%) C AISI 4150 (std.) Sample 0.48-0.53 0.489 Mn 0.75-1.00 0.789 P < 0.035 0.021 S < 0.04 0.002 Cr 0.75-1.2 0.851 Mo 0.15-0.25 0.177 Si 0.15-0.3 0.192
The samples were annealed at approximately 900 oC for 1 hr. and subsequently cooled in different media: furnace cool, air cool, water cool and oil cooled. In addition, one of the samples was cooled in salt bath at 350 oC for 1 hr and then cooled in water. Three observations for each treatment were conducted. Seebeck coefficients, relative to Seebeck coefficient of copper, of each sample were measured after heat treatment. The configuration of the Seebeck coefficient apparatus was demonstrated in figure 1. The absolute Seebeck coefficient was calculated by the equation:
Sa = V + S Cu T
(1)
where S a , S Cu , V and T are absolute Seebeck coefficient (V/K), Seebeck coefficient of copper (V/K), induced voltage difference (V) and temperature difference, respectively. The temperature at the cold side is about 26 oC and temperature difference between hot and cold
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sides in this experiment was set at 4 oC. Seebeck coefficient of copper at 300 K is 1.83 V/K [1].
Figure 1: Diagram of Seebeck coefficient measurement apparatus
Next, hardness and microstructures of the samples were investigated by hardness test Rockwell scale C with loading of 150 kgf and optical microscope. The crystal structures of each sample were also examined by D-8 Bruker x-ray diffractometer using Cu-K as x-ray source, step width of 0.02 degree and step time of 0.04 s.
Results and discussion
Hardness and Seebeck coefficient Harnesses and Seebeck coefficients of as-received samples and heat-treated low alloy steels after quenching with different media were shown in figure 2. Negative Seebeck coefficient pointed out that electron is carrier responsible for thermoelectric power of the samples. According to Vedenikov [8], Seebeck coefficient of pure iron at 300 K is approximately +12
V/K. However, Seebeck coefficient of steel is perturbed by element in solid solution,
microstructure, dislocation and precipitates [5, 6]. Among these contributions, contribution from solute atom is the greatest because solute atoms act as new diffusion centers for electron [5]. The contribution from solute atom to Seebeck coefficient, S i , obeys the linear law as shown by:
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S i = K i C i
(1)
where Ki and Ci are the specific thermoelectric power per weight percent of solute element i (V/(K-wt%)) and amount of solute element i (wt.%), respectively. The value of Ki depends on various factors such as chemical composition, texture, grain size, etc [6]. For example the
KC varies from -20 to -52 V/K-wt% depending on carbon contents [5-7]. The higher the
carbon content, the lower is the KC value. KCr and KMn were reported as -0.30 and -3 V/Kwt%, respectively. Beside contribution from solute element, the contribution from dislocation also leads to negative Seebeck coefficient [5]. The sign of change of Seebeck coefficient due to contribution from microstructure relies on type of phase transformation. For example, amount of retain austenite in martensitic stainless steel leads to positive Seebeck coefficient with specific thermoelectric power constant of +0.087 V/K-wt% [7]. It can be seen that the magnitude of specific thermoelectric power due to microstructure is less than those of solute atom in the order of magnitude; therefore, the negative Seebeck coefficient of steel is expected.
Figure 2: Hardness and Seebeck coefficients of as-received sample and heat treated low alloy steels after quenching in different media
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Figure 2 also demonstrates dependent of Seebeck coefficient on quenching media or cooling rate. When cooling rate is high, e.g. quenching in oil or water, magnitude of Seebeck coefficient decreases and hardness increases. This phenomenon may be used to establish relationship between Seebeck coefficient and hardness. It is well known that for fast cooling rate carbon atoms do not have enough time to diffuse out of the austenite to form equilibrium microstructure of pearlite. Consequently, depending on cooling rate, non-equilibrium structures such as bainite or martensite will form and hardness of quenched sample increases. The effect of cooling rate on Seebeck coefficient may be explained by crystal structure and microstructure as discussed later. XRD-result Effect of cooling rate on crystal structure can be seen by x-ray diffraction pattern demonstrated in figures 3 and 4. From these figures, crystal structures of quenched samples can be sorted into two groups: 1) samples quenched at low and moderate cooling rate and 2) samples quenched at high cooling rate. Figure 3 demonstrated that crystal structure of sample with low cooling rate is body center cubic with diffracted planes: (110), (200) and (211). In addition, (200) and (211) peaks tend to disappear when cooling rate is high. When considering at (110) peak (figure 4), (110) peaks of water-quenched and oil quenched samples are shifted from those of the other samples. In addition, they are broader than those of samples quenched at low and moderate cooling rate. The shift of the peak indicates that crystal structures of the oil and water quenched sample are different from the other samples and the broader peaks indicates occurrence of lattice distortion during fast cooling. As shown in figure 2, magnitude of Seebeck coefficients of oil cooled and water cooled samples are lower than those of other samples. The reduction of the magnitude of Seebeck coefficient may be due to phase change and lattice distortion. The distortion reduces electron movement; consequently, magnitude of Seebeck coefficient decreases. This explanation can also be applied when the Seebeck coefficients and x-ray diffraction patterns of only oil quenched and water quenched samples are compared. However, rather than chemical composition, crystal structure is not only a factor affecting Seebeck coefficient. To explain variation of Seebeck coefficients of asreceived, furnace cooled, air quenched samples and of sample quenched in salt bath, microstructure analysis is needed.
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Figure 3: X-ray diffraction pattern of as received sample and quenched samples
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Figure 4: [110] peak of as received sample and quenched samples
Microstructure Microstructure of each sample was shown in figure 5. From this figure, microstructures of oil quenched and water quench sample are martensite with some ferrite. It is well known that dislocation density of sample quenched with high cooling rate is very high. As a result, hardness of these samples is high. The dislocation not only increases hardness, it also impedes electron transport. Therefore, rather than the effect of structure distortion, magnitudes of Seebeck coefficients of oil quenched and water quenched samples are reduced by the existing dislocation.
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(a)
(b)
(c)
(d)
(e)
(f)
Figure 5: Microstructures of samples: a) as received, and heat-treated sample with different quenching media: b) furnace, c) air, d) saltbath, e) oil and f) water at magnification of 500x
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Figure 5 also points out the presence of ferrite and pearlite in samples cooled in furnace. For as-received sample and samples cooled in air and salt bath, microstructure of these samples consists of ferrite and cementite. Unlike microstructure of furnace cooled sample, the ferrite and cementite of these samples are not lies in lamellar order as illustrated in figure 6. The nonlamellar array of ferrite and cementite is classified as bainite [9]. In addition, cementite in as-received, air cooled and salt bath cooled samples disperses all over microstructure. Consequently, hardness of these samples is higher than that of furnace cooled sample. Although microstructure of furnace cooled sample is different from those of as-received and air quenched sample, their Seebeck coefficients are not significantly different. The reason may be because the phases (ferrite and cementite) present in these samples are the same. However, this is not conclusive and more investigation is needed. Seebeck coefficient data and XRD result also point out that although crystal structures of as-received sample and of samples quenched in air and salt bath are the same, magnitude of Seebeck coefficient of sample quenched in salt bath is higher than those of the other samples. The higher magnitude of Seebeck coefficient may be due to larger grain size. Theoretically, grain boundary behaves as an obstacle for electrical transport. The increasing of magnitude of Seebeck coefficient due to increasing grain size was also found by Caballero et al [7].
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(a)
(b) Figure 6: Microstructures of samples cooled in a) furnace cooled and b) salt bath at magnification of 1000x
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Conclusions
Seebeck coefficients and hardness of quenched low alloy steels, AISI 4150, were studied. Although Seebeck coefficient depends on crystal structure and microstructure, hardness of samples cannot be directly related to Seebeck coefficient. Hardness of these steels can be explained directly by their microstructures. In contrast, explanation of Seebeck coefficient by microstructure is more complicate. Magnitude of Seebeck coefficient of quenched samples is influenced by phases present in sample and grain size.
References
(1) Blatt F.J., Schroeder P.A., Foiles C.L. and Greig D.L., 1976, Thermoelectric Power of Metals, Plenum Press, New York (2) N.F. Mott and Jones H., 1936, The Theory of the Properties of Metals and Alloys, Dover Inc., New York, 310 (3) Kasap, S., 1996, Thermoelectric Effects in Metals: Thermocouples [Online], Available : http://www.materials.usask.ca/samples/Thermoelectric-Seebeck.pdf [September 9, 2009] (4) Brahmi, A. and Borrelly, R., 1997, Study of Aluminium Nitride Precipitation in Pure Fe-Al-N Alloy by Thermoelectric Power Measurements, Acta Materialia, 45, 18891897 (5) Lavaire, N., Merlin, J. and Sardoy, V, 2001, Study of Ageing in Strained Ultra and Extra Low Carbon Steels by Thermoelectric Power Measurement, Scripta Materialia,
44, 553-559.
(6) Massardier, V., Lavaire, N., Soler, M. and Merlin, J., 2004, Comparison of the Evaluation of the Carbon Content in Solid Solution in Extra-mild Steels by Thermoelectric Power and by Internal Friction, Scripta Materialia, 50, 1435-1439. (7) Caballero, F.G., Capdevila, C., Alvarez, L.F. and Garca de Andrs, C., 2004, Thermoelectric power studies on a martensitic stainless steel, Scripta Materialia, 50, 1061-1066. (8) Vedernikov M.V., 1969, Adv. Physics., 18, 337 (9) Krauss G., 1990, Steel: Heat Treatment and Processing Principles, ASM international, Ohio, U.S., pp.78
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Corrosion Assessment of Carbon Steel in Thailand by Atmospheric Corrosion Monitoring (ACM) Sensors
Wanida Pongsaksawada, Ekkarut Viyanita, Sikharin Sorachota, and Tadashi Shinoharab
a
National Metal and Materials Technology Center (MTEC), Pathumthani, Thailand, Tel.: 0-2564-6500 Fax: 0-2564-6338 Email: wanidap@mtec.or.th
b
National Institute for Materials Science, Ibaraki, JAPAN Tel: +81-298-59-2604 Fax: +81-298-59-2601
Abstract Atmospheric corrosion of metal depends on material compositions, weather condition (dry, dew, and rain period), temperature, relative humidity, and airborne sea salt of specific location. General testing procedure to obtain the corrosion rate is by actual exposure test of the specimen panels based on time interval plan. In Japan, atmospheric corrosion monitoring (ACM) sensor, made of an iron-silver galvanic couple, has been developed and used to sense the corrosivity in terms of galvanic current. Under some atmospheric conditions, these data can be converted to time of wetness and related to the corrosion rate of carbon steel. With ACM sensors, it is possible to monitor the corrosion rate in a shorter time than the exposure test. To apply the ACM sensors in Thailand, it is necessary to evaluate the effectiveness and correlation between the actual corrosion rate and the sensor output. In this research during June 2007 May 2009, we performed exposure tests of carbon steel (JIS SS400) along with ACM sensors under outdoor and sheltered conditions at three locations: (1) Rama VI Road, Bangkok (2) Suvarnabhumi International Airport, Samutprakarn and (3) Royal Thai Navy Dockyard, Chonburi, representing urban, airport, and marine environments, respectively. Weather data were obtained from temperature, relative humidity, and ACM sensors. To estimate the corrosion rate, weight loss measurements were carried out on specimens exposed for 1 month period over 2 years. Average monthly weight loss ranks from high to low as marine, airport, and urban environments. The relationship between outdoor corrosion rate and ACM output is found to be linear on a log-log scale at airport and urban test stations during March 2008 May 2009.
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Keywords Atmospheric Corrosion, ACM sensor, Carbon steel
1. Introduction Atmospheric corrosion of metal is governed by chemical composition of thin film electrolyte on the metal surface which is dependent on air pollutants, humidity, and temperature. Corrosion scientists in several countries have been carried out exposure tests to investigate the effects of the environment on corrosion rates (Pourbiax (1982), and the corrosion resistance of different materials (Chen et al. (2005), De La Fuente et al. (2007), Singh et al. (2008), Sun et al. (2009), Tahara et al. (2005), and Veleva et al. (2009)). The actual field tests usually take 10-20 years for an evaluation period. To accelerate the experimental study, simulated wet-dry cyclic tests have been performed for qualitative observation (Han et al. (2007) and Katayama et al. (2005)). Electrochemical measurement such as AC impedance monitoring sensor has been incorporated into the atmospheric corrosion tests by Nishikata et al. (2005), Shitanda et al. (2007), Wall et al. (2005) to enhance the understanding of corrosion process and monitor quantitative parameters as a function of environmental factors. Another electrochemical measurement by atmospheric corrosion monitoring (ACM) sensor relates galvanic current with corrosion rate. The impedance and ACM sensors have been applied to monitor the corrosion in industrial plants and infrastructure. In Japan, ACM sensor, made of Fe-Ag galvanic couple, has been developed and used to monitor the corrosivity of various atmospheric conditions in the work of Motoda et al. (1994) and Shinohara et al. (2006). Linear relationship between outdoor corrosion rate and sensor galvanic current output was found at severe marine and rural/marine environments in Japan (Shinohara et al. (2006)). In Thailand, atmospheric corrosion tests had been conducted on organic-coated carbon steel by Bhamornsut et al. (2003), zinc by Phantor et al. (2003), and stainless steel by Daopiset et al. (2008). This present research is the first to apply the ACM sensor in atmospheric corrosion study of structural steel in Thailand. The exposure tests of the test panels as well as the ACM sensors were carried out from June 2007 May 2009 at three different environmental conditions. Weight losses and sensor outputs were evaluated.
2. Experimental procedures Exposure test stations were selected for this field study. The details at each site are described in Table 1.
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Table 1 Structural steel plates (JIS SS400) were cut into rectangular coupons with dimension of 150mm x 70mm x 6mm. Blue oxide scales were removed by HCl acid, sandblasting, and mechanical polishing. The initial weights of the samples were recorded. Exposure tests were carried out in open-air (outdoor) and under shelter (indoor) conditions for 1 and 12 months. The tests were repeated for 24-month period. An ACM type corrosion sensor was installed on each test rack and connected to a data logger (Syrinx Inc.). Picture of a test station is illustrated in Fig. 1. The ACM sensors were replaced every month. Temperature and humidity sensors were installed under a cover at each location and connected to the data logger. Electrical current (Q), temperature (T), and relative humidity (RH) were recorded in a memory card every 10 minutes. After the test, specimen panels and data were collected for analyses. Two specimens were cleaned according to ASTM G01 to remove corrosion products. The average weight loss was determined. Monthly results were related to the sensor data to evaluate correlation with ACM sensor. Annual results were fitted to a multiple linear regression model as a function of environmental parameters. Figure 1
3. Results and discussion Short term exposure test Monthly results from June 2007 November 2008 were reported in the previous work (Pongsaksawad et al. (2009)). With additional data from December 2008 May 2009, the average monthly weight losses over two years are summarized in Table 2. Corrosivity ranks from high to low as marine, airport, and urban atmosphere or in the increasing distance from the sea shore as expected. The sheltered environments are typically less corrosive than open air condition as seen by smaller magnitude of average corrosion losses. The corroded sheltered specimens were influenced only by dew condensation, temperature, relative humidity, sea salt and air pollutants, whereas the specimens exposed outdoor were influenced by rain fall as well. However, during some months in rainy season, the sheltered samples were more severely corroded than outdoor samples due to rain wash affect that removes corrosive species from the metal surface. Table 2
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Correlation between corrosion rate and sensor output Corrosion rates of one month exposure test were plotted as a function of the ACM sensors output to evaluate their relationships. For sheltered condition, the corrosion rates were related to the daily average electricity (Q). The best correlation (R = 0.7220) was observed at urban site during March 2008 April 2009 as shown in Fig. 2(a) as: log CRurban [mmpy] = 0.165 log Q [C/day] 0.658 (1) No correlation was found at marine and airport test sites. In case of outdoor environment, the current during rain period (Qrain) is much higher than dew period (Qdew). Thus the effective sensor output (Qeff) is defined as Qeff =Qdew + Qrain, where is 0.2 [Shinohara 2004]. As shown in Fig. 2(b), the relationship between corrosion rate and effective sensor output for urban site has a strong positive correlation (R = 0.7113) during March 2009 May 2009 and follows the expression: log CRairport, urban [mmpy] = 0.183 log Qeff [C/day] 1.056 (2) No correlation is observed for marine exposure sites. In the atmospheric corrosion study with this Fe-Ag type ACM sensor in Japan (Shinohara et al. (2006)), the ACM sensors could be used to estimate the atmospheric corrosion rate in severe marine and rural/marine conditions, but not in the mild marine atmosphere. Thailand has less temperature fluctuation and longer time of wetness, which may require another type of ACM sensor for marine environment. Further study by using a long life ACM sensor is under consideration. Figure 2 Multiple linear regression model The conventional method to predict the corrosion rate is by finding an empirical relationship with the active environmental parameters such as in the atmospheric corrosion study of Vietnam by Hong Lien et al. (2009). The simplest model is a multiple linear function. Generally, one year exposure tests are conducted and repeated to obtain reliable sampling data. In this study, two sets of one year exposure tests were carried out at each test station during June 2007 to May 2009. The average corrosion rates of each phase and other environmental parameters are reported in Table 3. Table 3 Based on our one year exposure test data shown in Table 3, the best correlation suggests that the outdoor corrosion rate (CR) is a function of temperature, relative humidity, and total rain time as: CR [g/ m2 / y] = 446.9 - 11.850 T [C ] + 0.535 RH [%] + 0.028 Train [h/ y] (3)
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Temperature has a negative affect on corrosion rate. Higher temperature causes the water droplet on the specimen surface to evaporate; thereby, the corrosion rate is reduced. Both relative humidity and total rain time have positive affects on corrosion rate due to increasing time of wetness. Time of rain slightly contributes to corrosion because it also washes away the corrosive residues. The calculated corrosion rates (Eq. 3) were plotted against the actual values as shown in Fig. 3 with R = 0.9733. However, other dependent variables such as SO2 and Cl- ions were not taken into account since they were not monitored during the exposure period. Figure 3 Comparing the two correlation methods discussed above, the ACM sensor is applicable for corrosion prediction at airport and urban environments. With the use of ACM sensor, corrosion rate can be monitored in real time without the need to conduct a long-term field test. For marine site, the multi-variable model can be applied.
4. Conclusions (1) The atmospheric corrosion of structural steel decreases with increasing distance from the coast (marine > airport > urban). (2) In Thailand, the atmospheric corrosion of structural steel under sheltered environment is generally less corrosive than that under outdoor environment. The rain wash affect is not a major contribution. (3) The corrosion losses can be estimated by the ACM sensor output at airport and urban test station. (4) The outdoor corrosion losses at marine, airport, and urban atmosphere increases with decreasing temperature, increasing relative humidity, and increasing time of rain.
5. Acknowledgement The authors gratefully acknowledge the financial support from the National Metal and Materials Technology Center (MTEC), Thailand and the technical support from the National Institute for Materials Science (NIMS), Japan.
6. References Bhamornsut, C., L. Chotimongkol, R. Nakkuntod, S. Suphonlai, T. Kodama, and H. Tanabe, Atmospheric
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Degradation of organic coatings in Thailand, Proc. of Japan Society of Corrosion Engineers Conference, November 16-21, 2003, Japan. Chen, Y.Y., H.J. Tzeng, L.I. Wei, L.H. Wang, J.C. Oung, H.C. Shih, Corrosion resistance and mechanical properties of low-alloy steels under atmospheric conditions, Corrosion Science, 47, (2005) 10011021. Daopiset, S., P. Wanaosod, T. T. Xuan Hang, and T. Anh Truc, Atmospheric corrosion of stainless steels 304 and 316 with different surface finishes, Proc. of the 5th Thailand Materials Science and Technology Conference, September 16-19, 2008, Thailand. De La Fuente, D., J.G. Castano, M. Morcillo, Long-term atmospheric corrosion of zinc, Corrosion Science, 49, (2007) 14201436. Han, W., G. Yu, Z. Wang, J. Wang, Characterization of initial atmospheric corrosion carbon steels by field exposure and laboratory simulation, Corrosion Science, 49, (2007) 29202935. Hong Lien, L. T., P. Thi San and H. Lam Hong, Atmospheric corrosion of carbon steel in Vietnam: The relationship between corrosion rate and environmental parameters and the classification of atmospheric corrosivity of carbon steel, Proc. of Japan Society of Corrosion Engineers Conference, May 22-24, 2009, Japan, A305. Katayama, H., K. Noda, H. Masuda, M. Nagasawa, M. Itagaki, K. Watanabe, Corrosion simulation of carbon steels in atmospheric environment, Corrosion Science 47 (2005) 25992606. Motoda, S., Y. Suzuki, T. Shinohara, Y. Kojima, S. Tsujikawa, W. Oshikawa, S. Itomura, T.Fukushima and S.Izumo, Zairyo-to-Kankyo, 43, (1994), 550. Nishikata, A., F. Suzuki, T. Tsuru, Corrosion monitoring of nickel-containing steels in marine atmospheric environment, Corrosion Science, 47, (2005) 25782588.
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Panther, B. C., M. A. Hooper, G. P. Ayers, I. Cole, W. Limpaseni, W. Somboon, F. Veersai, W. Veersai, Atmospheric depositions and corrosion Impacts in Bangkok, Proc.of the 2nd Regional Conference on Energy Technology Towards a Clean Environment, February 12-14, 2003, Phuket, Thailand, Vol. 2, pp. 675-683. Pongsaksawad, W., S. Sorachot, J. Troset, E. Viyanit, and T. Shinohara, Applying atmospheric corrosion monitoring sensor for carbon steel under various exposure test sites in Thailand , Proc. of Japan Society of Corrosion Engineers Conference, May 22-24, 2009, Japan, A304. Pourbaix, M., The Linear Bilogarithmic Law for atmospheric corrosion, Wiley, New York, (1982), 107. Shinohara, T., A. Tahara and Y. Hosoya, Datasheets of Atmospheric Corrosion behaviors of low alloyed steels with corrosivities at exposure test sites, Proc. of the 3rd International Conference on Advanced Structural Steels, Aug 22-24, 2006, Korea. Shitanda, I., A. Okumura, M. Itagaki, K. Watanabe, Y. Asano, Screen-printed atmospheric corrosion monitoring sensor based on electrochemical impedance spectroscopy, Sensors and Actuators, B 139, (2009) 292297. Singh, D.D.N., S. Yadav, J. K. Saha, Corrosion of low carbon steel in atmospheric environments of different chloride content, Corrosion Science, 50, (2008) 93110. Sun, S., Q. Zheng, D. Li, J. Wen, Long-term atmospheric corrosion behaviour of aluminium alloys 2024 and 7075 in urban, coastal and industrial environments, Corrosion Science, 51, (2009) 719727. Tahara, A., T. Shinohara, Influence of the alloy element on corrosion morphology of the low alloy steels
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exposed to the atmospheric environments, Corrosion Science, 47, (2005) 2589 2598. Veleva, L., M. Acosta, E. Meraz, Atmospheric corrosion of zinc induced by runoff, Corrosion Science, 51, (2009) 20552062. Wall, F.D., M.A. Martinez, N.A. Missert, R.G. Copeland, A.C. Kilgo, Characterizing corrosion behavior under atmospheric conditions using electrochemical techniques, Corrosion Science, 47, (2005) 17-32.
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Table 1. Locations of exposure test sties
Environment
Location
Description Onthegroundfacingthe
Marine
SattahipNavyDockyard,Chonburi GulfofThailand Onthegroundnearbythe
Airport
SuvarnabhumiInternationalAirport,Samutprakarn
runwayandindustrial district Ontherooftopofa7story
National Science and Technology Development Agency, Urban Bangkok heavytraffic buildinginfluencedby
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Table 2. Average monthly weight losses of outdoor and sheltered conditions Weight Loss (g/ m2) sheltered Marine June 07 May 08 June 08 May 09 Airport June 07 May 08 June 08 May 09 Urban June 07 May 08 June 08 May 09 46.476 44.535 39.452 37.793 28.280 30.867 outdoor 57.786 55.614 56.333 48.472 38.286 46.567
Location
Phase
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Table 3.
Corrosion rate of one- year exposure test and environmental parameters: CR [g/ m2 / y] 137.381 167.857 n/a 165.238 110.238 99.048
temperature (T), relative humidity (RH), and time of rain (Train). Site Marine Airport Urban Phase June 07 May 08 June 08 May 09 June 07 May 08 June 08 May 09 June 07 May 08 June 08 May 09 T [C] 29.187 28.305 29.302 28.761 31.7668 32.490 RH [%] 66.010 55.079 58.140 48.594 55.807 40.281 Train [h/ y] 269.833 1089.667 975.833 802.167 524.167 428.667
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ACM sensor
Figure 1 ACM sensor and structural steel coupon on an outdoor test rack
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(a) Urban sheltered environment
(b) Airport and urban outdoor environment
Figure 2 Linear correlations between monthly corrosion rate and effective sensor output were found at (a) urban sheltered condition (March 2008 April 2009) and (b) airport and urban outdoor condition (March 2008 May 2009).
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250 Calculated CR [g/ m / y] 200 150 100 50 0 0 50 100 150

2
R = 0.9474 R = 0.9733
200
250
Actual CR [g/ m / y]
Figure 3 Calculated values compared to the actual values
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Pickling Behavior of AISI 304 Stainless Steel in Sulfuric and Hydrochloric Acid Solutions
W. Homjaboka, S. Permpoonb, G. Lothongkuma
a
Department of Metallurgical Engineering, Faculty of Engineering, Chulalongkorn University, Patumwan, Bangkok 10330, Thailand Email: whomjabok@yahoo.com, Gobboon.L@chula.ac.th
b
Thainox Stainless Public Company Limited, 324 Moo 8, Highway no. 3191 Road, Tambol Mabkha, Nikom Pattana, Rayong 21180, Thailand
Abstract Oxide scales are formed on AISI 304 stainless steel surface during high temperature processing as well as a Cr-depleted layer, which grows between the oxide scale and base metal. Pickling is an important process that includes mechanical and chemical operations, used to remove oxide scales, Cr-depleted layer and to recover the surface passivity. The multi-step pickling is commonly used because of its higher efficiency than a single step pickling. In this study, the multi-step pickling of AISI 304 stainless steel in HCl solution was investigated instead of H2SO4 solution for the first step of pickling. HF+HNO3 mixed acid is traditionally used in the second step. The pickling mechanism of HCl and H2SO4 was discussed based on weight loss and the pickled surface qualities. It was found that pickling efficiency in the first step directly affects the surface qualities of the final pickled sample. HCl solution showed much lower pickling efficiency than H2SO4 solution. This resulted in high remaining oxide scale and intergranular attack at the Cr-depleted layer, which cannot be completely removed in the second pickling step. Increasing of HCl concentration and electrolytic current were not enough to improve its pickling efficiency. The addition of small amount H2O2, which is a strong oxidizing agent, significantly improves the pickling efficiency of HCl. A smooth surface without any oxide scale and free of intergranular attack can be obtained. Keywords: Pickling; Hydrochloric acid; Scale; AISI 304 Stainless steel
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1. Introduction Acid pickling is an important step for production of cold rolled stainless steel plate. It is aimed to remove the oxide scale as well as a Cr-depleted layer growing between the oxide scale and the base material. Oxide scale and Cr-depleted layer are formed during high temperature processing. Removing oxide scale processes consist of mechanical descaling and pickling. In mechanical descaling, scale breaker and shot blasting were used to break up the oxide scale. This results in easily penetration of pickling solution into oxide scale and enhances the pickling efficiency [1-5]. Multi-step pickling is used for pickling process because it has higher efficiency and better surface quality than single step [6-7]. In the first step, electrolytic was used for increase pickling efficiency [8]. In this step, the mechanism is that the solution penetrates into metal Cr-depleted layer and the oxide scale is undercut and removed [6]. The acid type and concentration has strong influence on surface finish quality. In the second step, HNO3+HF has become widely accepted and used for removal remaining oxide scale and passivation [8]. The sequence at which the pickling steps are used influences the surface finish significantly. H2SO4 is a cheap acid and has a good pickling efficiency, which can be improved by using with electrolytic, so that, H2SO4 with electrolytic is general used for the first step. However, H2SO4 pickling causes black smut forming. Even though black smut can be removed by HNO3+HF in the next step, but the surface finish has high roughness and intergranular attack. In this study, the multi-step pickling behavior of AISI 304 austenitic stainless steel in HCl solution was experimented for replacing H2SO4 solution in the first step and the HNO3+HF mixed acid solution was used traditionally in the second step. HCl pickling has a uniform dissolution behavior with no intergranular attack [8-10]. Results were discussed based on weight loss and surface finish of the pickled samples.
2. Experimental 2.1. Material AISI 304 austenitic stainless steel strips were hot-rolled downs to a thickness of 3 mm. The chemical composition of this material is listed in Table 1. After mechanical descaling process, test samples of 25x50x3 mm were cut. Then, only unexposed area was painted with EPIGEN XD005 (acid-resistant at high temperature), and clean with acetone and ethanol. The test samples were finally dried with air and kept in a desiccator before experiment.
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Table.1 Chemical composition (wt.%) of AISI 304 stainless steel used in this study, analyzed by OES
Element C Cr Ni Mn Content 0.04 18.1 8.03 1.076 Element Si P S Fe Content 0.342 0.029 0.001 Balanced
2.2. Pickling To prepare the HCl, H2SO4, HF and HNO3 electrolytes, analytical grade was used. Purity 50%H2O2 was used in this study. During pickling, temperature was controlled constantly in a water bath with constant stirring. After pickling, the samples were rinsed with tap water and brush for removal any reaction products. The pickling conditions were acid concentration of 1.0, 2.0, 3.0, 4.0, 5.0 and 6.0 M at 60C or 85 C depending on the purposed tests.
2.3. Characterization The surface finish was characterized with roughness profiler (Telescan 150) for surface roughness. Optical microscope (OM) at 200X and scanning electron microscopy (SEM) at 3000X were used for remaining oxide level analysis. Fig.1 showed the evaluation of remaining oxide on sample surface after the in-house standard.
Fig.1Remaining oxide evaluation after the in house standard on 6 areas observation on test sample surface at 200X.
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3. Results and discussion HCl solution was investigated instead of H2SO4 solution for the first step of pickling. HF+HNO3 mixed acid solution was still traditionally used in the second step. The traditional and studied conditions for this experiment were showed in Fig. 2. The total weight loss resulting from those multi-step pickling conditions (Fig. 2) was shown in Fig. 3. The weight loss of H2SO4 condition was high but some oxide scale remains on pickled surface in level 2 as shown in Fig. 4a. Pickling by H2SO4 solution with electrolytic followed by HNO3+HF solution increased the weight loss and allowed achieving a surface finish free of any oxide scale as shown in Fig. 3 and 4b.
Fig.2 Multi-step pickling of AISI 304 stainless steel between the traditional and studied conditions.
Fig.3 Total weight loss of multi-step pickling of AISI 304 stainless steel in H2SO4 at 85C or HCl at 85C followed by HNO3+HF at 45C.
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In case of HCl pickling instead of H2SO4 pickling, it showed that HCl had lower pickling efficiency than H2SO4 (Fig. 3) and much oxide scale remained (Fig. 4c). Increasing HCl concentration and HCl pickling with electrolytic did not result in increasing the pickling efficiency to be higher than H2SO4 pickling efficiency. The surface finish of HCl pickling had rougher surface and more intergranular attack than H2SO4 pickling as shown in Fig. 4d. The result was not the same as report by L.-F. Li and J.-P. Celis [9], which said that uniform dissolution and no intergranular attack were observed by HCl pickling.
4.0 M H2SO4 (Electrolytic); 85C followed by HNO3+HF; 45 C
4.0 M H2SO4; 85C followed by HNO3+HF; 45 C
Roughness (Rq) = 3.29 m Remaining oxide level 2
c followed by HNO3+HF; 45 C
4.0 M HCl; 85C
4.0 M HCl (Electrolytic); 85C
d followed by HNO3+HF; 45 C
Fig.4 SEM surface characterization of AISI 304 stainless steel after multi-step pickling
To understand mechanism of pickling by both HCl and H2SO4 in the first pickling step, which has a significant effect on the final surface finish after HNO3+HF pickling, the step by step of
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weight loss was analyzed as shown in Fig. 5 and the surface was characterized by SEM as shown in Fig. 6. HCl pickling had much lower weight loss than H2SO4 pickling and both samples surface were covered with oxide scale (Figs. 6a and 6b). HCl pickling had smooth surface compared with H2SO4 pickling. After the second pickling step with HNO3+HF, HCl pickling had higher weight loss than H2SO4 pickling and the intergranular attack became more pronounced on surface finish (Fig. 6d).
Fig.5 Step by step weight loss of AISI 304 stainless steel after pickling in 4.0 M H2SO4 at 85C or 4.0 M HCl at 85C followed by HNO3+HF at 45C
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4.0 M H2SO4; 85C
4.0 M HCL; 85C
4.0 M H2SO4; 85C followed by HNO3+HF; 45 C
4.0 M HCl; 85C followed by HNO3+HF; 45 C
Fig.6 SEM surface characterization of AISI 304 stainless steel after multi-step pickling with conditions same as in Fig. 5
According to the previous results (Fig. 5 and 6) and discussion, the evolution of surface during multi-step pickling in H2SO4 and HCl solutions followed by HNO3+HF can be described as in Fig. 7a and 7b, respectively. The original metal surface consists of oxide scale, Cr-depleted layer and base metal. On H2SO4 pickling in the first step, H2SO4 transports into oxide scale. Then, the Cr-depleted layer is attacked or dissoluted. Finally, the oxide scale is removed by
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undercutting. Most oxide scale but only some Cr-depleted layer is removed. The surface is rough because H2SO4 pickling behavior is non-uniform dissolution. The next step pickling by the selective dissolution of HNO3+HF, intergranular attack appears. Remaining oxide scale and Cr-depleted layer are almost removed. The final surface finish is completely free of oxide scale. The evolution of surface finish after pickling in HCl followed by a pickling in HNO3+HF is showed in Fig. 7b. The same mechanism as H2SO4 is obtained. However, HCl has lower pickling efficiency than H2SO4. Most of all oxide scale and Cr-depleted layer still remain. The observed surface is smooth because HCl pickling behavior is uniform dissolution. By HNO3+HF pickling in the second step, intergranular attack appears because of a selective dissolution on remaining Cr-depleted layer.
a. H2SO4; 85C
Oxide scale Cr-depleted layer
b. HCl; 85C
Oxide scale
Base Metal
Base Metal
Initial Surface
Base Metal
Base Metal
First step
Intergranular attack
Base Metal
Intergranular attack
Base Metal
Second step Fig.7 The multi-step pickling mechanism models of intergranular attack.
According to the mechanism, the most important finding is that the surface finish obtained from multi-step pickling is greatly affected by the pickling efficiency of the first step. Multistep pickling will successively allow achieving a smooth surface finish free of any oxide scale, when a high enough pickling efficiency with uniform dissolution in the first step is available. From the result, increasing of HCl concentration and electrolytic currents were not enough to
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improve its pickling efficiency to be more than the H2SO4 efficiency. The addition of H2O2, which is a strong oxidizing agent, possibly improved the pickling efficiency of HCl. The temperature for this study must be fixed at 60C because H2O2 decomposes at temperature over than 60C.
. Fig.8 Step by step weight loss of AISI 304 stainless steel by pickling with HCl at 60C or HCl+H2O2 at 60C or H2SO4 (Electrolytic) at 85C followed by HNO3+HF at 45C.
Addition of H2O2 to improve pickling efficiency of HCl in the first step resulted in increasing weight loss and having an affect on the second step pickling by HNO3+HF by decreasing weight loss, as shown in Fig. 8. It also reduced intergranular attack and delivered smooth surface finish as shown in Fig. 9. Multi-step pickling was successive at 10g/L H2O2 added to HCl solution. It allowed achieving a higher pickling efficiency than H2SO4 efficiency, smooth surface finish free of oxide scale, and no intergranular attack
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4.0 M H2SO4 (Electrolic); 85C followed by HNO3+HF; 45 C
4.0 M HCl; 60C followed by HNO3+HF; 45 C
4.0 M HCl+10g/L H2O2; 60C followed by HNO3+HF; 45 C
d 4.0 M HCl+10g/L H2O2; 60C
followed by HNO3+HF; 45 C
Fig.9 SEM surface characterization of AISI 304 stainless steel after pickling in H2SO4, HCl, HCl + H2O2 solutions followed by HNO3+HF at 45C
4. Conclusions The multi-step pickling of AISI 304 stainless steel in HCl solution as the first step followed by HNO3+HF as the second step was investigated. The mechanism models of pickling by HCl or H2SO4 in the first step were proposed. The following conclusions can be drawn from this study. 1. HCl solution has lower pickling efficiency than H2SO4 solution.
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2. HCl solution can not completely remove Cr-depleted layer and oxide scale. 3. H2O2 addition can improve pickling efficiency of HCl solution. The addition of 10g/L H2O2 is enough to deliver the smooth surface without any oxide scale and free of intergranular attack after HNO3+HF pickling.
5. Acknowledgement The authors would like to thank the Research and Development Center of Thainox Stainless Public Company Limited for test samples, discussion and analysis equipment. The thanks also go to the Thailand Research Fund (TRF) and the Office of Small and Medium Enterprises Promotion (OSMEP) for the research fund.
6. References [1] Lacombe, B. Baroux and G. Beranger, Stainless Steel, 1st edition., Les Editions de Physique Les Ulis, France, 1993. [2] Stainless Steel, ASM Specialty Handbook, 1996. [3] Mars G. Fontana. Corrosion Engineering, 3rd edition, McGraw-Hill International Editions, Materials Science and Engineering Series, Singapore, 1987. [4] Denny A. Jones. Principles and Prevention of Corrosion, 2nd edition, Prentice Hall International, Inc, Singapore, 1997. [5] Suwaree Ratanamongkolthaworn, Effects of sulfuric acid concentration, temperature, ferrous and ferric ion contents on pickling behavior of AISI 304 stainless steel, Master Thesis in Metallurgical Engineering, Chulalongkorn University, 2007. [6] L.-F. Li, P. Caenen, M. Daerden, D. Vaes, G. Meers, C. Dhondt, and J.-P. Celis, Mechanism of Single and Multiple Step Pickling of 304 Stainless Steel in Acid Electrolytes, Corrosion Science, Volume 47, 2005, pp. 1307- 1324. [7] L.-F. Li and J.-P. Celis, Intergranular corrosion of 304 stainless steel pickled in acidic electrolytes. Scripta Materialia, Volume 51, Issue 10, 2004, pp. 949-953. [8] L.-F. Li, Pickling of Austenitic Stainless Steels. Internal review report Alz-Arcelor France, 2002. [9] L.-F. Li and J.-P. Celis, Effect of hydrochloric acid on pickling of hot-rolled 304 stainless steel in iron chloride-based electrolytes, Corrosion Science, Volume 50, 2008, pp. 804-810.
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[10] L.-F. Li, Pickling and re-pickling of stainless steel with UGCO and UG3P+H2SO4 electrolytes. Internal review report Alz-Arcelor France, 2002.
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The Effect of Welding Speed and Tool Pin Profile on Metallurgical and Mechanical Properties of Joining of Semi-Solid (SSM) Aluminium Alloy A356 by Friction Stir Welding Process (FSW)
Thongchai Kruepue a and Prapas Muangjunbureeb
a, b
Department of Mining and Materials Engineering, Faculty of Engineering, Prince of Songkla University, Hatyai, Songkla, 90112 Thailand Tel: 074 287323 Fax: 074 212897 E-mail : Kruepue@Yahoo.co.th
Abstract The effect of joining parameters and tool pin profile on microstructure and mechanical properties of semi-solid metal A356 joints produced by friction stir welding was investigated. In this work, the joints were made by using a fixed rotating speed of 1,750 rpm with varying welding speed of 80, 120 and 160 mm/min. In addition, Two different types of tool pins, cylindrical and square pin, were applied. The Scanning electron microscope (SEM) reveals fine microstructure and uniform dispersion of Si (Silicon) particles obtained from cylindrical pin than that of square pin. Transverse and longitudinal tensile strengths obtained from cylindrical pin are greater than square pin. Furthermore, the joint made from 1,750 rpm, 160 mm/min with cylindrical pin shows highest strength. Key words : Semi-solid metal A356, Welding parameter, Thermo-mechanical affected zone, Stir zone
1. Introduction There are two types of semi-solid forming technology at the present. Rheo casting is one of them. It involves the preparation of semi-solid metal (SSM) slurry from liquid alloys and casting the slurry into a die for component manufacturing. In this work, semi solid metal was obtained from a new Rheo casting technique called Gas Induced semi-solid (GISS) [1]. It was clear that the joint between cast Al alloy has increasingly expanded in the usage of casting component in automotive such as suspension, driveline and engine parts. Conventional fusion welding of SSM aluminum die casting alloys is generally difficult due to the formation of blowholes in weld. In addition, the microstructure is also altered. Therefore, a new welding method is required to overcome theses problems. In recent year, friction stir
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welding (FSW) was developed as a solid state joining process in which materials are joined by the frictional heat as shown in Fig.1 (Thomas : TWI). This process is effective for the welding of aluminum alloys. However, only a limited number of studies have been carried out on SSM cast aluminum alloys. The aim of this work is to evaluate the effect of joining parameters on the microstructure and mechanical properties of the welded SSM A356 alloys in as cast condition.
Fig.1 Showing the friction stir welding
2. Experimental The material used in this study was SSM (Semi-Solid Metal) A356 Al alloy 100 mm in length, 50 mm in width and 4 mm in thickness. The chemical composition is listed in Table 1. In this study, the two different tool pin profiles as shown in Fig. 2, a tool with a cylindrical pin and a tool with a square pins, were applied. The length of the pin was 3.2 mm, and the diameter of the pin was 5 mm. The shoulder of the tool was 20 mm/min. The friction stir welding (FSW) has many welding parameters, such as tool rotating speed, welding speed and the angle of the tool. In this work, only the welding speed was changed from 80, 120 and 160 mm/min. Other parameters were fixed at 1,750 rpm of tool rotating speed and 30 of tool angle. The welding tool was rotated in the clockwise direction and specimens, which were tightly fixed at the backing plate, were traveled. The test pieces were cut in the cross-section direction, ground, polished and etched, with Kellers reagent. Some of the necessary photographs were taken by optical microscopy (OM), scanning
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electron microscope (SEM) with energy dispersive x-ray analysis (EDX) examinations. The Vickers hardness profile of the weld zone was measured on a cross-section and perpendicular to the welding direction using a Vickers indenter with a 100 gf load for 10 s and 0.6 mm distance from welding center. The tensile test was carried out at room temperature using an Instron-type testing machine with cross-head speed of 1.67x10-2 mm s-1. The shapes and location of the specimens for test are shown in Fig.3. Two kinds of tensile test specimens were prepared from the welded specimens. One is transverse to the weld zone and the other is longitudinal to the weld zone.
Table 1 chemical composition of SSM A356 Al alloy (wt.%) Metal A356 Si 7.74 Fe 0.57 Cu 0.05 Mn 0.06 Mg 0.32 Zn 0.01 Ti 0.05 Cr 0.02 Ni 0.01 Al Bal.
Cylindrical
Square
Fig.2 showing two different tool pin profiles
Fig.3 Locations of the test specimens (A) Discard, (B) Microstructure, (C) Tensile test and (D) Microstructure and Hardness test
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3. Results and discussion
3.1 Effect of the temperature of friction stir welding The geometry of the tools pin affects the heat generation and the flow of the plastic material. The temperature results of FSW joints are shown in Fig. 4 (a), (b). Zone 1 is the heat generation increases from the downforce about 28 s., zone 2 is the heat generation decreases from the stop downforce about 20 s. and zone 3 is the heat generation increases from the welding speed. It demonstrate, that the welding temperatures during FSW decrease in the high welding speed. On the top surface, the welding temperatures are almost the same for two tool types. However, the temperature for three welding speeds of cylindrical pin is higher than that of the square pin. Therefore, for the cylindrical pin, the frictional area between the tool pin and the welding material is higher than that of the square pin [7].
(a) The temperature of cylindrical pin
(b) The temperature of quare pin
Fig.4 showing the temperature generation results of the friction stir welding
3.2 Effect of the pin geometry on the weld surface appearance of the FSW Fig.5 shows the surface appearance of the friction stir welded sample obtained from cylindrical and square tool pins with various welding speeds at 1750 rpm. The top surface of the joints indicate smooth surface particularly for the higher welding speeds. However, the welding flash appears at the retreating side of the weld zone where the direction of the tool rotation moves oppositely to the travel direction for every condition.
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10 mm
10 mm
(a) 80 mm/min
(d) 80 mm/min
10 mm
10 mm
(b) 120 mm/min
(e) 120 mm/min
10 mm
10 mm
(c) 160 mm/min
(f) 160 mm/min
Fig. 5 showing the photos of weld surface appearance
3.3 Effect of the tools pin geometry on the macro cross-section of the FSW Fig. 6 illustrates the macro cross-section photos of the welded joints. Free-defect joint can be obtained using two different tool pin profiles. There were no voids, cracks or other weld defects, just as shown in Fig. 6 (a)-(f). An elliptical stir zone with an onion ring structure was generated for the cylindrical pin. There was a macroscopically visible banded structure for the square pin. However, shaped band structure appeared to dominate the advancing side without appearing on the retreating side.
TMAZ
SZ
TMAZ
A BM
1 mm
TMAZ
SZ
TMAZ
A BM
1 mm
(a) 80 mm/min
(d) 80 mm/min
1 mm
1 mm
(b) 120 mm/min
(e) 120 mm/min
1 mm
1 mm
(c) 160 mm/min
(f) 160 mm/min
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Fig. 6 Macro cross-section of the welded joint, (SZ) stir zone, (TMAZ) thermal-mechanical affected zone, (R) retreating, (A) advancing
3.4 Microstructure of joint
(a) Base metal of SSM A356 Al alloy
(b) R-TMAZ of cylindrical pin
(c) A-TMAZ of cylindrical pin
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(d) R-TMAZ of square pin
(e) A-TMAZ of square pin
(f) SZ of cylindrical pin
(g) SZ of square pin
Fig.7 Optical microstructure of the welded joint, (SZ) Stir zone, (TMAZ) Thermal-mechanical affected zone, (R) Retreating, (A) Advancing
3.4.1 Optical microstructure of FSW The spheroidal grain microstructure of the BM from Fig. 7 (a) is composed of primary
phase (white region) and Al-Si eutectic structure (black region). The TMAZ of cylindical
pin and the square pin from Fig. 7 are formed besides the SZ, which are divided into the (b, d) R-TMAZ and the (c, e) A-TMAZ is depending on the different microstructures at each zone. The sharp transition between the BM and the SZ is observed in the retreating side. The compression similar grain structures and a narrow range of deformed structures are observed at the R-TMAZ. The slightly elongated grain structures or tention similar and a wider range of deformed structures are observed at the A-TMAZ. The microstructure of the SZ is very different from that of the BM. The spheroidal grain structure disappeared and finer Si particles are dispersed over the whole stir zone. There are no voids, cracks or other welded defects can be observed.
3.4.2 SEM microstructure of FSW The microstructure of the BM from Fig. 8 (a) is composed of primary phase and Si particles structure (Elongated plate), are distributed partially in the primary phase and
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formed eutectic structure. The TMAZ of cylindical pin and the square pin from Fig. 8 are formed besides the SZ, which are divided into the (b, d) R-TMAZ and the (c, e) A-TMAZ which depend on the different microstructures. The smaller Si particles structures are observed for the R-TMAZ and A-TMAZ of the cylindrical pin. However, the finer Si particles are homogeneously dispersed in the SZ of the cylindrica pin than the square pin and the plate-like particles disappear. The plate-like Si particles may be broken into slightly finer particles by the stirring of the welding tool [6, 11]. This is due to the cylindrical pin generates higher friction than that of the square pin. More heat input can improve the flow of the plastic material. The material transports from the advanced side to the retreated side, and goes around the pin, back to the advanced side.
(a) Base metal of SSM A356 Al alloy
(b) R-TMAZ of cylindrical pin
(c) A-TMAZ of cylindrical pin
(d) R-TMAZ of square pin
(e) A-TMAZ of square pin
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(f) SZ of cylindrical pin
(g) SZ of square pin
Fig.8 shows the SEM microstructure of the welded joint, (SZ) Stir zone, (TMAZ) Thermal-mechanical affected zone, (R) Retreating, (A) Advancing
3.5 Effect of the pin geometry on the tensile strength
Table 2 Tensile test results from transverse direction Tensile test (MPa) Welding speed (mm/min) Cylindrical Failuer locatio n 80 120 160 176.22 190.85 193.89 Base Base Base 143.23 171.73 173.61 Square Failuer locatio n Weld Weld Base
Fig. 9 Showing the tensile strength of the transverse direction with various welding speeds.
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3.5.1 The transverse tensile strength of the FSW Table 2 and Fig. 9 Show the transverse tensile strength of the friction stir welding. The tensile strength of the joints increases with the welding speed increases for two different tools pin. The highest tensile strength of the joints was obtained from the cylindrical pin. However, for each welding speed, the cylindrical pin indicates higher transverse tensile strength. This is because the finer Si particles are homogeneously dispersed in the SZ of the cylindrical pin than that of the square pin.
3.5.2 The longitudinal tensile strength of the FSW Table 3 and Fig. 10 Show the longitudinal tensile strength of the friction stir welding. The tensile strength of the joints increases with the welding speed increases for two different tools pin. The highest tensile strength of the joints was obtained from the cylindrical pin. However, for each welding speed, the cylindrical pin indicates higher transverse tensile strength. This is because the finer Si particles are homogeneously dispersed in the SZ of the cylindrical pin than that of the square pin. In comparison, the longitudinal tensile strength are higher than transverse tensile strength in each parameter for both tool pins. Table 3 Tensile test results from longitudinal direction Welding speed (mm/min) 80 120 160 Tensile test (MPa) Cylindrical 172.57 190.79 222.23 Square 170.67 179.83 193.67
Fig. 10 Showing the tensile strength of the longitudinal direction with various welding speeds.
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4. Conclusions (1) The geometry of the tools pin affects the heat generation. It demonstrates that the welding temperatures during FSW decrease in the high welding speed. The temperatures for three welding speeds of cylindrical pin are higher than the square pin. (2) Free-defect joint can be obtained using two different tool pin profiles. There were no voids, cracks or other weld defects. (3) The finer Si particles are homogeneously dispersed in the SZ of the cylindrical pin than that of the square pin. (4) The transverse and longitudinal tensile strengths of the joints increase with the welding speed increases for two different tools pin. The highest tensile strength of the joints was obtained from 160 mm/min welding speed of the cylindrical pin.
Acknowledgments This work was financially supperted by TRF. In addition, the authors would like to thank Department of Mining and Materials Engineering, Faculty of Engineering, Prince of Songkla University, Hatyai, Songkla, Thailand.
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References [1] J. Wannasin Development of a Novel Semi-Solid Metal Processing Technique for Aluminium Casting Applications [2] R. Akhter. et al., (2006) Effect of pre/post T6 heat treatment on the mechanical properties of laser welded SSM cast A356 aluminium alloy, vols 116-117, PP.173- 176 [3] Yeong-Maw Hwang, (2007) Experimental study on temperature distributions within the workpiece during friction stir welding of aluminum alloys [4] Yan-hua, et al., (2005) The influence of pin geometry on bonding and mechanical properties in friction stir weld 2014 Al alloy [5] K. Kumar (2007) The role of friction stir welding tool on material flow and weld formation A 485 (2008) 367374 [6] W.B. Lee et al., (2003) The improvement of mechanical properties of friction-stirwelded A356 Al alloy Material Science and Engineering A356 (2003) pp. 154159 [7] Hidetoshi Fujii et al., (2005) Effect of tool shape on mechanical properties and of friction stir welded aluminum alloys
microstructure
[8] Z.Y. Ma, et al., (2006) Effect of friction stir processing on the microstructure of cast A356 aluminum [9] Y.G. Kim. et al., (2006) Effect of Welding parameter on Microstructure in stir zone of FSW joints of Aluminum die casting alloy Material Science and Engineering A 415 (2006) 250-254 [10] K. Elangovan et al.,) 2007( Influences of tool pin profile and welding speed on the formation of friction stir processing zone in AA2219 aluminium alloy [11] M.L. Santella . et al.,) 2005( Effects of friction stir processing on mechanical properties of the cast aluminum alloys A319 and A356 Scripta Material 53 (2005) 201206
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Rheocasting of aluminum alloys by the Gas Induced Semi-Solid (GISS) process

R. Burapa, S. Janudom, R. Canyook, J. Wannasin* Department of Mining and Materials Engineering, Faculty of Engineering, Prince of Songkla University, Hat Yai, Songkhla, 90112, Thailand *Corresponding author, e-mail: jessada.w@psu.ac.th
Abstract A new semi-solid metal processing technique has been developed to produce semi-solid slurry with more effectiveness and efficiency at lower costs for the rheocasting process. This technique is called the Gas Induced Semi-Solid (GISS) process. The GISS process has been successfully used in laboratory settings to process several aluminum alloys, including cast and wrought alloys. However, to develop this technique for commercial applications in industrial settings, it is important to determine the optimized processing conditions in order to control the resulting slurry temperature and microstructure of the alloys. In this work, the effects of rheocasting temperatures and rheocasting times on the resulting slurry temperature and microstructure of A356 aluminum alloy were investigated. The results indicate the suitable conditions of the GISS process are longer rheocasting time and lower rheocasting temperature. These conditions result in the formation of fine and uniform globular structure of the primary -Al phase. Keywords: Aluminum alloy; Semi-solid metal; Gas Induced Semi-Solid process; Rheocasting; Globular structure
1. Introduction Aluminum alloys have been widely used in many applications such as electronic and automotive components. These aluminum components are mainly produced by die casting. In a conventional die casting process, molten metal is injected into a die cavity resulting in turbulent flow and entrapment of air inside the casting parts. The consequences are oxide films and porosity defects, which cause several quality issues and lower the mechanical properties of the components.(1) One way to improve these problems is to apply the semisolid metal (SSM) forming technology. SSM forming is a forming process of metal in the
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semi-solid state. In addition, the metal is modified during solidification to have nondendritic or globular grain structure. One technique for SSM forming is to create semisolid slurry directly from the melt and then to form the slurry into parts. This forming technique is called rheocasting.(2) In recent years, there are various rheocasting processes that have been developed to produce semi-solid slurries. These processes include the New Rheocasting (NRCTM) process by UBE Machineries, Inc. (Japan),(3) the Advanced SemiSolid Casting Technology by Honda (Japan),(4) the Semi-Solid Rheocasting (SSRTM) by IdraPrince Inc. (USA),(5) the Sub Liquidus Casting (SLCTM) by THT Presses, Inc. (USA),(6) the Swirl Enthalpy Equilibration Device (SEED) by Alcan (Canada)(7), and the RheoDiecasting (RDC) process by Brunel University (England).(8) Although several processes are successfully used in the industry, they are still quite complex and have high capital costs. As a result, a simple and efficient rheocasting process which offers lower costs for producing semi-solid slurry is needed.(9) Recently, a new rheocasting process has been developed at the Department of Mining and Materials Engineering, Prince of Songkla University, Thailand. This process is called the Gas Induced Semi-Solid (GISS).(9) This process uses the principle of applying a combination of localized heat extraction between a cold rod and the molten metal with vigorous convection during the initial stages of solidification to produce non-dendritic or globular grain structure.(2) The GISS process can be applied with a large number of cast and wrought alloys such as A356, ADC10, ADC12, 2024, 6061 and 7075. To utilize the process effectively and efficiently, it is important to understand the effects of the key processing parameters. In this study, the effects of the rheocasting temperatures (the liquid metal temperatures before starting the introduction of gas bubbles) and the rheocasting times (the time to introduce gas bubbles) on the resulting slurry temperature and microstructure of A356 alloy were investigated.
2. Materials and Experimental Procedures The aluminum alloy used in this study was a commercial cast aluminum alloy A356, which has a wide solidification range with the solidus and liquidus temperature of 557C and 613C, respectively. The chemical composition of this alloy is listed in Table 1. Table 1. Chemical composition (wt%) of the aluminum A356 alloy used in this study. Si 6.9 Fe 0.42 Cu 0.05 Mn 0.04 Mg 0.42 Zn 0.01 Ti 0.10 Al Bal.
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The GISS process is illustrated schematically in Figure 1. Figure 2 shows the prototype of the GISS slurry maker used in this study. The machine consists of a graphite diffuser, a thermocouple, a system to control the inert gas flow rate, a system to control the air cooling and a central control unit.
Thermocouple Flow meter
Graphite diffuser Molten metal Inert gas bubbles Crucible
Inert gas
Figure 1. Schematic of the GISS process.(2)
Figure 2. The prototype of the GISS slurry maker used in this study. For all the experiments, the temperature of the graphite diffuser was kept at 40C, the diffuser surface area per the melt volume (S/V ratio) was set at 0.35, and the gas flow rate was controlled at 4 liters/minute. In the experiments, the aluminum alloy was first melted in a graphite crucible using an electric resistance furnace. The molten metal was fluxed at 710C before the experiments. Then, about 500 grams of the melt was ladled out of the crucible using a stainless steel cup coated with a ceramic coating. Subsequently, a thermocouple was inserted near the middle of the melt to record the temperature data during the experiments. When the melt cooled down to the set rheocasting temperature, a porous graphite diffuser was immersed and fine nitrogen gas bubbles were introduced into the melt. Then, the graphite diffuser was removed from the semi-solid slurry, and the slurry was allowed to cool in air until the temperature reached 580 C (about 45% solid
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fraction). The semi-solid metal was removed from the cup and quenched in water. Samples were cut from the same position from the quenched semi-solid metals. Figure 3 shows the schematic location of the samples. The samples were then prepared by a standard grinding and polishing procedure, and were then etched with the Kellers reagent. The microstructure of the samples was observed and analyzed using an optical microscope. In this study, the experimental conditions investigated include the rheocasting temperatures and rheocasting times of 620, 635, and 650 C, and 5, 12, 20 seconds, respectively.
Middle
Figure 3. Schematic of the samples and the position of the micrographs.
3. Results and Discussion Representative cooling curves and the procedure to determine the slurry temperature after the GISS process is shown in Figure 4. For example, the graphite diffuser was immersed at the rheocasting temperature of 650 C and with the introduction of nitrogen gas bubbles for the rheocasting time of 20 s. When the bubbling was stopped and with a few seconds of delay, the slurry temperature was determined from the curve. Following this analysis, the slurry temperatures for different rheocasting temperatures and rheocasting times were acquired and summarized in Figure 5.
660 650 640 630 Temperature (C) 620 610 600 590 580 570 0
Start immersion of graphite diffuser at 650C Check temperature of semi-solid slurry The semi-solid slurry was quenched in water at 580C
Stop immersion of graphite diffuser. Rheocasting time = 20 seconds

20 40 60 80 100 120 140 160 180 200 220 240 260 Time (s)
Figure 4. Representative cooling curves of A356 alloy and the procedure to determine the semi-solid slurry temperature.
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618 616 Slurry temperature (C) 614 612 610 608 606 604 602 0
Rheocasting temp. at 620 C Rheocasting temp. at 635 C Rheocasting temp. at 650 C
Liquidus temperature = 613C
10
15
20
25
Rheocasting time (s)
Figure 5. The effects of rheocasting temperatures and rheocasting times on the slurry temperature of A356 aluminum alloy. Then, the results from the various slurry temperatures were converted to solid fraction (fs) data. The Scheils equation was used to estimate the solid fraction.(2) For A356 alloy, the calculation assumed a binary alloy, linear liquidus and solidus lines and the partition coefficient (k) equals 0.13. Figure 6 shows the solid fraction of A356 slurry under a combination of rheocasting temperatures and rheocasting times.
20 18 16
Solid fraction (%)
Rheocasting temp. at 620 C Rheocasting temp. at 635 C Rheocasting temp. at 650 C
14 12 10 8 6 4 2 0
0 5 10 15 20 25 Rheocasting time (s)
Figure 6. The effects of rheocasting temperatures and rheocasting times on the solid fraction of aluminum A356 alloy. The GISS process utilizes the cold graphite diffuser and the introduction of fine nitrogen gas bubbles to decrease the temperature of the melt below its liquidus temperature. The
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rheocasting temperature and rheocasting time affect the slurry temperature and, consequently, the solid fraction with the relationships shown in Figures 5 and 6, respectively. To create more solid phase in the melt, the rheocasting temperature is lowered and the rheocasting time is increased. The obtained data give the important processing information about the required rheocasting times to achieve a certain amount of solid fraction in the melt with different starting rheocasting temperatures. For example, to achieve about 5% solid fraction in the melt, the rheocasting times should be about 7, 9, and 15 seconds for the rheocasting temperatures of 620, 635, and 650 C, respectively. The microstructure of aluminum A356 alloy solidified without the application of the GISS process showing coarse dendritic structure is given in Figure 7. The white phase in Figure 7 is primary -Al phase and the dark continuous matrix is the quenched eutectic phase. The typical microstructures of A356 alloy produced by the GISS process under the rheocasting time of 5 seconds for various rheocasting temperatures are shown in Figure 8. The experimental results show that the primary -Al phase varied with the solidification conditions from coarse dendritic, to rosette-like, and to globular structure.
Figure 7. Microstructure of aluminum A356 alloy solidified under normal conditions showing coarse dendritic microstructure. The experimental results for the case of rheocasting time of 5 seconds show that with the rheocasting temperature of 650 C, the primary -Al phase has rosette-like morphology, as shown in Figure 8(a). With the rheocasting temperatures of 635 C and 620 C, as shown in Figures 8(b) and 8(c), respectively, the primary -Al phase consists of mostly globular and some rosette-like grains. Figure 9 shows the experimental results under different rheocasting times at the same rheocasting temperature of 620 C. With the rheocasting time of 12 seconds, most of the primary -Al phase appears globular with some rosettelike structure, Figure 9(a). When the rheocasting time increases to 20 s, the morphology of
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primary -Al phase is mainly globular with a uniform distribution in the structure, Figure 9(b).
(a)
(b)
(c)
Figure 8. Microstructures of A356 alloy produced by the GISS process under the rheocasting time of 5 seconds for different rheocasting temperatures: (a) 650 C; (b) 635 C; and (c) 620 C.
(a)
(b)
Figure 9. Microstructures of A356 alloy produced by the GISS process under the rheocasting temperature of 620 C for different rheocasting times: (a) 12 s and (b) 20 s. These results suggest that the primary -Al phase tends to be fine globular structure with a uniform distribution in the eutectic phase when the rheocasting temperature is decreased and rheocasting time is increased. The results may be explained by the dendrite fragmentation mechanism.(10) The non-dendritic structure is developed from a large number of initial dendrite fragments going through the ripening mechanism which results in globular grain structure. For the GISS process, the results obtained in this study suggest that a combination of localized heat extraction with the introduction of fine nitrogen gas bubbles through the graphite diffuser to create the vigorous convection during immersion of the graphite diffuser in the molten metal causes dendrite arms to break off from the mother dendrites. This process helps to generate secondary nuclei particles, which then can grow to form a non-dendritic or globular structure within a few seconds. With the lower
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rheocasting temperature, the mother dendrites will be finer making it easier and faster for the dendrite arms to be detached. In addition, with longer rheocasting times, more dendrite arms will be detached and the longer ripening time will lead to more globular structure.
4. Conclusions 1. This study gives important information for processing about the required rheocasting times to achieve a certain amount of solid fraction in the melt with different starting rheocasting temperatures. 2. Fine and uniform globular structures for aluminum A356 alloy were obtained when the rheocasting temperature was low and the rheocasting time was long. 3. The GISS process can be used to produce semi-solid slurries effectively and efficiently when the proper processing conditions are selected.
5. Acknowledgements The authors would like to thank the Reverse Brain Drain Project (RBD), the National Science and Technology Development Agency (NSTDA) for funding this research project. In addition, we would like to thank Mr. Thiensak Chucheep and Innovative Metal Technology (IMT) Team for helping with the experiments.
6. References 1. de Figueredo A, Ed. 2001. Science and Technology of Semi-Solid Metal Processing. The North American Die Casting Association, U.S.A. 2. Wannasin, J. and Thanabumrungkul, S. 2008. Development of a semi-solid metal processing technique for aluminium casting applications. Songklanakarin J. Sci. Technol., 30(2): 215-220. 3. Kaufmann, H., Wabusseg, H. and Uggowitzer, P.J. 2000. Metallurgical and Processing Aspects of the NRC Semi-Solid Casting Technology. Aluminum, 76(1-2): 70-75. 4. Kuroki, K., Suenaga T., Tanikawa, H., Masaki, T., Suzuki, A., Umemoto, T. and Yamazaki, M. 2004. Establishment of a Manufacturing Technology for the High Strength Aluminum Cylinder Block in Diesel Engines Applying a Rheocasting Process. Proceedings of the 8th International Conference on Semi-Solid Processing of Alloys and Composites, Limassol, Cyprus.
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5. Yurko, J., Martinez, A. and Flemings, M. 2003. The Use of Semi-Solid Rheocasting (SSRTM) for Automotive Casting. SAE 2003 World Congress & Exhibition, Detroit, Michigan, U.S.A. 6. Jorstad, J., Thieman, M. and Kamm, R. 2004. Fundamental Requirements for Slurry Generation in the Sub Liquidus Casting Process and the Economics of SLCTM Processing. Proceedings of the 8th International Conference on Semi-Solid Processing of Alloys and Composites, Limassol, Cyprus. 7. Douter, D., Hay, G. and Wales, P. 2004. SEED: A New Process for Semi-Solid Forming. Canadian Metallurgical Quarterly, 43(2): 265-272. 8. Fan, Z., Fang, X. and Ji, S. 2005. Microstructure and Mechanical Properties of RheoDiecast (RDC) Aluminium Alloys. Mater. Sci. Eng. A, 412(1-2): 298-306. 9. Wannasin, J., Junudom, S., Rattanochaikul, T. and Flemings, M.C. 2008. Development of the Gas Induced Semi-Solid Metal Process for Aluminum Die Casting Application, Solid State Phenomena Vols. 141-143: 97-102. 10. Wannasin, J., Martinez, R.A. and Flemings, M.C. 2006. Grain refinement of an aluminum alloy by introducing gas bubbles during solidification. Scripta Materialia. 55: 115-118.
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Effects of replacing binder with powder space holder on properties of metal injection moulded foam
U. Koikula , A. Manonukulb,*, S. Suranuntchaia
King Mongkuts University of Technology Thonburi, Pracha-U-Thit Rd., Thungkru, Bangkok, 10140.
National Metal and Materials Technology Center, 114 Thailand Science Park, Paholyothin Rd., Klong Luang, Pathumthani, 12120. *E-mail: anchalm@mtec.or.th (Corresponding author)
Abstract Metal foam can be produced using metal injection moulding with powder space holder. In this study, the effects of volume fraction of spacer holder on the foam properties were studied. Spherical poly (methyl methacrylate) (PMMA) particles were used as a space holder material. The 30% volume fraction of stainless steel 316L powder was mixed with varied volume fractions of binder and PMMA. There were five volume fractions of PMMA, which are 30% to 50% with an increment of 5%. The results shown that the volume fraction of PMMA affected the properties. As the volume fraction of PMMA increased, the number of pore increased but the sintered density and the mechanical properties decreased. Keywords: metal foam; metal injection moulding; powder space holder
1. Introduction The interest in metal foam has significantly increased due to their extended applications, for example, automotive parts, filters, cushions, insulators and biomedical implants (Degischer and Kriszt, 2002). Currently, there are different manufacturing methods for metal foams. The conventional process is the gas injection method, where gas bubbles are injected into a liquid metal. The liquid metal is transferred using a conveyer belt to solidify. This process is very effective in continuously producing large size foams, but it is difficult to control the process to obtain a uniform structure. Another process is the deposition method, which starts from the ionic state of metal and deposits a polymeric foam preform with open cells. Similar to the deposition method, the investment casting
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method also uses a polymeric foam perform. In the investment casting method, the polymeric foam preform is dipped into graphite slurry or coated with a thin layer by metal vaporisation. Subsequently, the polymeric foam preform is removed by thermal treatment (Ashby et al., 2000). These two processes can produce a complex shape part, that can be fabricated by preforming the polymeric foam but both methods are expensive (Gibson and Ashby, 1988). Metal injection moulding (MIM) is a manufacturing process combining the traditional powder metallurgy process and plastic injection moulding (German, 1997). It is capable of producing small parts with complex shape in a mass production scale. Hence, MIM using powder space holder (MIM-PSH) has been developed for producing complex metal foam part (Glsoy and German, 2008). The MIM with powder space holder for producing foam is similar to conventional MIM as shown in Fig. 1. There are four main steps, which are mixing, injection, debinding and sintering. In the first step mixing, metallic powder, binder and powder space holder are homogeneously blended together. The mixture is then granulated and injected to obtain green parts. The green part is heated to remove binder and powder space holder. This step is the debinding step and brown parts with the structure of foam are obtained after debinding. Brown parts are then sintered at a high temperature to obtain a metal foam. It is noted that MIM-PSH can produce both open-cell and close-cell foams. Poly (methyl methacrylate) (PMMA) is a common powder space holder. PMMA can be easily decomposed in the debinding stage and the metal foam with uniform foam structure can be manufactured by MIM-PSH (Glsoy and German, 2008). In addition, MIM-PSH can be cost-effective for microsized, highly complex porous shape with high dimensional accuracy (Williams, 2007). As a result, PMMA was used in this work as the powder space holder. Nishiyabu et al. (2008) studied the propertied of 316L foam produced by MIM with 30 and 60% volume fraction, and 10 and 40 m average size of PMMA. The effect of powder space holder shape was also studied (Jiang et al., 2005). Spherical and strip carbaminde particles were used as the powder space holder. Previous works only studied two volume fractions of powder spacer. Therefore, this work systematically investigated the effect of volume fraction of PMMA (powder space holder) on the properties of metal foam produced by MIM-PSH.
2. Experiment procedures
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In this work, the wateratomised stainless steel 316L powder (PF-20F) provided by Atmix Co. Ltd., Japan, was used. The powder has the average size of 10.5 m. PMMA was supplied by Sunjin Chemical Co. Ltd., Korea. PMMA was used as the powder space holder in this work and had a particle size of 84.7 m. Figure 2 shows the scanning
Figure 1: Schematic representation of metal injection moulding using powder space holder technique.
electron microscopy (SEM) images of the 316L powder and PMMA particle. The 316L powder is rounded, while the PMMA particle is spherical. The binder in this experiment comprised of three components: paraffin wax as a plasticiser, high density polyethylene as a backbone polymer and stearic as a acid surfactant. The binder reduces the viscosity of the feedstock and facilitates injection moulding. The backbone polymer provides the essential strength of the green parts. The surfactant strengthens the adhesion between binder and powder and weakens the agglomeration of the powder (Huang and Hsu, 2009).
(a)
(b)
Figure 2: SEM micrographs of (a) 316L powder and (b) PMMA particle.
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Stainless steel 316L powder, PMMA and a polyacetal-based binder were mixed together in five batches with different volume fractions as shown in Table 1. The solid loading of metal powder was kept constant at 30% volume fraction. The volume fraction of PMMA and binder were correspondingly varied with the constant combined volume fraction of 70%. The volume fraction of PMMA was increased from 30% to 50% in an increment of 5%, while the volume fraction of binder was decreased from 40% to 20% in an increment of 5%. Thus, the experiment was designed to replace binder with more PMMA, while the solid loading of metal powder was constant. This mixture was injected into tensile-test-specimen shape. Green parts were thermally debound at 450 C for 1 hour in air and sintered at 1100 C for 2 hours in an argon atmosphere. The densities of the green and sintered parts were measured. The sample were cut, mounted, grinded with silica papers and polished with diamond solution for the observation of microstructures using the optical microscopy. Hardness in HR15W scale and tensile tests were tested and reported.
Table 1. Fraction by volume of each component: PMMA, binder and metal powder. Volume fraction of PMMA (% vol) 30 35 40 45 50 Volume fraction of binder (% vol) 40 35 30 25 20 Volume fraction of metal powder (% vol) 30 30 30 30 30
3. Results and Discussion Processing parameters Most processing parameters for mixing and injection moulding were kept constant apart from the mixing and injection temperatures, which were varied with the volume fraction of PMMA. Figure 3 shows the variation of mixing and injection temperatures. The mixing and
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injection temperatures increased as the volume fraction of PMMA increased and the volume fraction of binder decreased. It is noted that the result for the 50% volume fraction of PMMA cannot be shown because it was not possible to inject the feedstock with 50% PMMA. From Table 1, a feedstock with 50% volume fraction of PMMA contained 30% by volume of metal powder and 20% by volume of binder. This means that during injection, there was only 20% liquid phase during injection (binder) and 80% solid phase during injection (PMMA and metal powder). This resulted in the high viscosity of feedstock and it was not possible to inject this feedstock with 50% volume fraction of PMMA regardless of the injection condition. As the volume fraction of PMMA increased, the viscosity of feedstock was higher and it was more difficult for the feedstock to flow. As a result, the higher mixing and injection temperatures were required to increase flow ability (Supati et al. 2000).
Figure 3: Mixing and injection temperatures as a function of the volume fraction of PMMA.
Density and microstructure Figure 4 shows the green and sintered densities as a function of volume fraction of PMMA. The sintered density is higher than the green density for all percentages of PMMA showing consolidation during sintering. The sample had similar green density because the volume fraction of metal powder was kept constant. The average green density of all specimens was 3.05 g.cm-3. The sintered density decreased with increasing volume fraction of PMMA. The sintered density of 3.58 g.cm-3 was observed in the 30% PMMA volume fraction, which is the highest sintered density. On the other hand, the sintered specimen with 45% PMMA volume fraction has the lowest sintered density of 3.49 g.cm-3.
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Figure 4: Green and sintered densities as a function of the volume fraction of PMMA.
The microstructures of the sintered 316L stainless steel specimens with four different volume fractions of PMMA are shown in Fig. 5. The number of pores depended on the PMMA contents. For all microstructures, the pores were introduced by the burnout of PMMA. All such pores retained the spherical shape of powder space holder and distributed homogeneously in the 316L stainless steel matrix. The number of pores increased with the increased addition of PMMA. The microstructure of 45% PMMA volume fraction exhibited a large number of pores distributed thoroughly inside the specimen as shown in Fig. 5 (d). There were more pores distributed in the microstructure of 45% PMMA volume fraction than the other volume fractions.
Mechanical properties Sintered metal foam was subjected to hardness and tensile tests. The hardness of metal foam specimens was tested using Rockwell W (HR15W). The hardness of sintered parts varied with the volume fraction of PMMA as shown in Fig. 6. The result shows that as the volume fraction of PMMA increased from 30% to 45%, the hardness decreased from 32-21 HR15W. The error was also displayed. The error increased as the volume fraction of PMMA increased. It is noticed that the 45% volume fraction of PMMA had the largest error and this volume fraction had a large number of pores. The microstructures of the specimens showed the number of pores increased with increasing volume fraction of PMMA. Therefore, the hardness values decreased as the number of pores in the specimens increased.
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(a) 30% vol PMMA
(b) 35% vol PMMA
(c) 40% vol PMMA
(d) 45% vol PMMA
Figure 5: Optical microstructure of sintered parts cross section as a function of the volume fraction of PMMA.
Figure 6: Hardness of sintered parts as a function of the volume fraction of PMMA
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Figure 7 shows the tensile strength and the elongation of sintered parts as a function of the volume fraction of PMMA. The tensile strength and elongation were dependent on the volume fraction of PMMA. As the volume fraction of PMMA increased, both tensile strength and elongation decreased. The 30% volume fraction of PMMA had the highest tensile strength of 125 MPa with 14% of elongation. The lowest values were obtained for the 45% volume fraction of the PMMA, which had the lowest tensile strength of 97 MPa and the elongation of 10%. The results are similar to the hardness results. The mechanical properties decreased with increased in porosity or the volume fraction of PMMA increased.
Figure 7: Tensile strength and elongation of sintered parts as a function of the volume fraction of PMMA
4. Conclusions Stainless steel 316L foams can be produced by applying a powder space holder method to a metal injection moulding process. The material used for space holding is a spherical PMMA particle. Five different volume fractions of PMMA were varied to replace the binder and the volume fraction of metal powder was kept constant. The experimental results show that the sintered density was higher than the corresponding green density. The sintered density decreased when the volume fraction of PMMA increased. The microstructure showed that the number of pore depended on the fraction of PMMA. The spherical shape pores were homogeneously dispersed in the 316L stainless steel matrix. The number of pores increased with increasing volume fraction of PMMA. Tensile strength, elongation and hardness decreased as the volume fraction of PMMA increased.
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5. References Ashby, M. F., Evans, A., Fleck, N.A. Gibson, L. J., Hutchinson, J. W. and Wadley, H. N. G. 2000.Metal Foam: A Design Guide. Butterworth-Heinemann. Boston. Degischer, H. P. and Kriszt, B. 2002. Handbook of Cellular Metals. Wiley. Weinheim. German R.M. and Bose, A. 1997. Injection Molding of Metals and Ceramics. MPIF. New Jersy. Gibson, L. J. and Ashby, M. F. 1988. Cellular Solids Structure & Properties. PERGAMON PRESS. Oxford. Glsoy, H.O. and German, R.M. 2008. Production of micro-porous austenitic stainless steel by powder injection molding. Scripta Materialia. 58: 295-298. Huang, M. Y. and Hsu, H. C. 2009. Effect of backbone on properties of 316L stainless steel MIM compact. Sci. Forum. 209: 981-984. Nishiyabu, K., Matsuzaki, S. and Tanaka, S. 2007. Net-Shape Manufacturing of Micro Porous Metal Components by Powder Injection Molding. Materials Science Forum. 534-536: 981- 984. Supati, R., Loh N.H., Khor, K. A. and Tor, S. B. 2000. Mixing and Characterization of Feedstock for Powder Injection Molding. Materials Letters. 46: 109-114. Williams, B., 2007. Powder injection moulding in the medical and dental sectors. Powder Injection Moulding International. 1: 12-19.
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Effect of temperature and pressure on the densification of titanium silicide compound

P. Thapnuya, S. Larpkiattaworna, T. Luangvaranuntb, J. Ikeuchia
a
Thailand Institute of Scienctific and Technological Research 35 Moo3 Technothani klong5 klongluang pathumthani
b
Chulalongkorn University Rama4 Road Pathumwan, Bangkok
Tel: 02-5779274 Fax: 02 -5774160-1 E-mail: choopacha@hotmail.com
Abstract Titanium silicide compound was synthesized from the mixture of titanium and silicon powder with atomic ratios of 60:40 and 70:30. The powders were mixed by ball milling and pressed by different methods: by using uniaxial pressing at 64 MPa, cold isostatic pressing (CIP) at 200 MPa, hot forging (HF) at 648 MPa, and hot pressing (HP) at 24 MPa. The samples were then sintered at 1300 oC or 1600 oC for 2 h. soaking time in argon atmosphere. The sintered samples were characterized for phases constitution using X-ray diffraction (XRD). Ti5Si3 was observed as main compound from both 60:40 and 70:30 mixtures. Archimedes method and scanning electron microscope (SEM) was used to measured density and investigate microstructure of sintered samples. It was found that the sample prepared from the 70:30 mixture has higher density than that sample of 60:40 mixture for all applied pressures. The density of samples prepared from the mixture of 70:30 and 60:40 sintered at 1300oC are in the range of 53-60% and 42-55%, respectively. It was found that densities of all samples sintered at 1300 oC were not much different when applied higher forming pressure by using CIP and HF. This means that pores are created during sintering. However the microstructure of samples formed by CIP and HF showed some big pore inside the sample body while sample formed at lower pressure by uniaxial press showed a more uniform pore size. By increasing the sintering temperature to 1600
o
C, the density of uniaxial pressed sample was increased to 85% and pore size get smaller
than the one sintered at 1300 oC. On the other hand, by applying a lower pressure during sintering the sample at 1600 oC by hot pressing, this can produce high density sample of 99% with a few amount of small closed pore. Keywords: Titanium silicide; Cold Isostatic Press; Hot Forge; Hot Press
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1. Introduction Titanium silicide compound such as TiSi3, TiSi2, TiSi, Ti5Si4 and Ti5Si3 can be prepared from various ratio of titanium and silicon metal. Among these silicide compounds, Ti5Si3 is known as an intermetallic compound which suitable for high temperature applications due to the properties of a high melting point (2130 C), moderate density (4.32 g/cm3), high temperature oxidation resistance, high hardness (11.3 GPa) and high young modulus (225 GPa) [1-2]. Titanium silicide can be prepared by a variety of powder techniques such as hot pressing, hot isostatic pressing, reactive sintering, mechanical alloying, and thermal or plasma spraying [3-6]. Due to the limited fracture toughness of Ti5Si3 at room temperature, most researchers have paid attention to produce multiphase in Ti5Si3 compound by addition of Al, C, Ni, or Nb [4, 6, 7]. However, Research works on densification of Ti5Si3 dependence on pressure and temperature are limited. In this paper, the variety of pressure and temperature were applied to prepare Ti5Si3, and then their density and microstructure were observed.
2. Experiment procedures Ti powder (99.7% purity, average particle size < 45m) and Si powder (99.7% purity, average particle size < 45m) were mixed in atomic ratio of 60:40 and 70:30 for 20 hr in Ar gas atmosphere. The mixed powder was compacted into specimens with 2 cm diameter and 0.5 cm thickness using different pressure of 64 MPa (uniaxial pressing), 200 MPa (cold isostatic pressing), 648 MPa (hot forging) and 24 MPa (hot pressing). The uniaxial pressed specimens were sintered at temperature varied from 1100 to 1600C. While other specimens were sinter at 1300 and 1600 C in argon atmostphere. The heating rate and soaking time were 15 C/min and 2 hr, respectively. The sinter specimens were measured for density by Archemidis method. X-ray diffractometer (XRD) and Scanning electron microscope (SEM) were used to determine the phase constitution and microstructure of the sintered specimens respectively.
3. Results and Discussion The sintered Ti: Si specimens of 60:40 and 70:30 were characterized for phase constitution by XRD as patterns shown in Figure.1 and 2 respectively. The results show that single phase of Ti5Si3 was formed in the 60:40 specimens sintered at temperature 1100-1500 C and at high temperature of 1600 C, TiC was observed together with Ti5Si3 phase. On the
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other hand, TiC can be formed together with Ti5Si3 in 70:30 specimens sintered at temperature range of 1100-1500 C and then this TiC phase will transform to Ti3SiC2 at 1600 C. The TiC and Ti3SiC2 phases in specimens could be from the diffusion of carbon inside the furnace into specimens during sintering process. Higher content of Ti in the specimen causes easier forming of TiC at low temperature and TiC will react with some Ti5Si3 to form Ti3SiC2 at high temperature.
Ti5Si3
TiC
1600 C
1500 C
Intensity
1300 C 1200 C
0
1100 C
25
30
35
40
45
50
55
60
65
70
75
80
Diffraction angle ( 2 )
Figure 1: XRD patterns of the Ti:Si mixture of 60:40 sintering at different temperatures
Ti5Si3 Ti3SiC2 TiC 16000C 15000C
Intensity
13000C
12000C 11000C
25
30
35
40
45
50
55
60
65
70
75
80
Diffraction angle ( 2 )
Figure 2: XRD patterns of the Ti:Si mixture of 70:30 sintering at different temperatures
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Table 1 shows density of specimens formed at different pressures after sintering at 1300C. It was found that increasing the forming pressure could slightly increase the density of specimen after sintering. The specimen with high Ti content yield higher density than that of lower Ti content which agree with the SEM micrographs in Figure 3 Moreover, Figure 3 shows that the specimens formed at higher pressure have bigger pore size than those formed at lower pressure. These phenomena can be explained that the Si vapor is trapped inside specimens which have been compacted at high pressure prior to sintering. On the other hand, Si vapor generated from specimens with lower forming pressure can easily move out during sintering before densification, and that results in smaller pores.
Table1 Density of Ti:Si mixture of 70:30 and 60:40 formed at various pressure and sintering at 1300C. (Bulk Ti:Si Bulk density Apparent density density/Apparent density) x100 60:40 Uniaxial press (63.69 MPa) CIP ( 200 MPa ) HF ( 648MPa ) 1.89 70:30 2.49 60:40 4.37 70:30 4.35 60:40 43.24 70:30 57.24
1.79 2.38
2.33 2.63
4.27 4.31
4.36 4.40
41.92 55.22
53.44 59.77
Table2 Density of TiSi mixture of 70:30 sintered at 1600C Apparent density (Bulkdensity/ Apparent density) x100 85.84 %Porosity by Archimedis method 14.16
Ti:Si
Bulk density
Uniaxial press (63.69 MPa) Hot press (24.24 MPa )
3.70
4.31
4.34
4.40
98.63
1. 37
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(a)
(b)
(c)
(d)
(e)
(f)
Figure.3 SEM micrographs of TiSi mixture of 60:40 and 70:30 formed at pressure (a) 60:40 (uniaxial Press 64 MPa), (b) 70:30 (uniaxial Press 64 MPa), (c) 60:40 (CIP 200 MPa), (d) 70:30 (CIP 200 MPa), (e) 60:40 (HF 648 MPa), (f) 70:30 (HF 648 MPa)
(a)
(b)
Figure 4: SEM micrographs of TiSi mixture of 70:30 sintered at 1600C formed by (a) uniaxial press at 64 MPa and (b) hot press at 24 MPa
According to Table 1 and Table 2, the density of specimen formed at 64 MPa increases significantly from 57% to 86%, when the sintering temperature is raised up from 1300 C to 1600 C. Furthermore, by simultaneously applying low pressure (24 MPa) and heating (1600 C) the density of specimens can be raise up to 99% which is shown in Figure 4.
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This means that temperature is more effective on increase in density than pressure; however applying pressure during sintering is the most effective to get high densification.
4. Conclusions Ti5Si3 can be synthesized from Ti and Si powders (70:30 and 60:40) sintered at 1100-1600 C. During sintering Si vapor can generated and form the pores inside specimen, and retards the densification. Increasing forming pressure is insignificant in densification during sintering. On the other hand, applying lower pressure during sintering can remarkably enhance the densification of Ti5Si3 specimens.
5. Acknowledgements The authors would like to thank Thailand Reasearch Fund (TRF), Nanoshield Ltd. and Japan International Cooperation Agency (JICA) for the support of this work
6. References [1] D.P. Riley,C.P. Oliver, E.H. Kisi. In-situ neutron diffraction of titanium silicide, Ti5Si3, during self-propagating high-temperature synthesis (SHS). Intermetallics 14 (2006) 33-38 [2] Massalski TB .et.al. Binary alloy phase diagrams.2nd ed.Materials Park, OH: ASM Int.:1990 [3] N.S. Stoloff. Materials Science and Engineering: A 261 (1999), 169-180 [4] A. Calka, A.P Radlinski, R.A.Shanks, and A.P. Pogany.Formation of titanium silicides by mechanical alloying .10 (1991), 734-737 [5] R.Mitra, Met.Meter.Trans.Microstructure and mecchanical behavior of reaction hot pressed titanium silicide and titanium silicide based alloys and composites.A 29A(1998), 1629-1641. [6] C.L.Yeh, W.H. Chen, and CC. Hsu. Formation of titamium silicides Ti5Si3 and TiSi2 by self-propagating combustion synthesis. 432 (2007), 90-95 [7] L.Zhang and J.Wu. Ti5Si3 and Ti5Si3base alloys: Alloying behavior, microstructure and mechanical property evaluation, Acta matter 46(10) (1998), 3535-3546
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Effect of aluminium on sintered properties of Cu-10wt%Sn bearing

V.Chobaomsup, T.Luangvaranunt
Department of Metallurgical Engineering, Faculty of Engineering, Chulalongkorn University, Phyathai Rd., Bangkok, Thailand 10330 Tel: +66 2218 6947, 089-128-1572 Fax: +66 2218 6942 Email:eng_mate@hotmail.com
ABSTRACT Self-Lubricating bearings are one of the oldest industrial applications of porous powder metallurgy part, dating back to the mid-1920. They remain the highest part produced by the P/M industry. The objective of this research was to study effect of sintering time, sintering temperature and ratio of adding aluminium on sintered properties of Cu-10wt%Sn bearing that produced from powder metallurgy processing. Various physical and mechanical properties such as density, percentage of porosity and hardness were tested to clarify the effect of processing parameters. Phase identification and microstructure were analyzed by X-Ray Diffractometer and optical microscope respectively. Sintering time in the experiment was 5, 30, 45, 60 and 90 min, sintering temperature was 830C and 900C and ratio of adding aluminium was 0wt%Al (no adding), 5wt%Al and 10wt%Al. It was found that the larger the addition of aluminium, the greater was the reduction in density and hardness in all sintering conditions. However, additional heat treatment after sintering, by isothermal annealing at 750oC for 1 h and quenching in water, increased the hardness of all specimens. The best processing condition to obtain high hardness was sintering at 900oC for 30 to 60 min, followed by isothermal annealing at 750oC and quenching in water. Keywords: Self-Lubricating Bearing; Cu-10wt%Sn; Powder metallurgy
1. Introduction Porous parts are divided into two groups, filters and self-lubricating bearing. Glass, ceramics and metallic materials can be used as the starting materials [1]. Nevertheless sintered metal powders has the best performance as starting materials, which has high strength, high thermal resistance, high corrosion resistance, durability and ease to control porosity and permeability. Self-lubricating bearings are one of the oldest industrial applications of porous P/M part, dating back to the mid-1920. They remain the highest part
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produced by the P/M industry. Metal powders used for porous parts are selected according to the application. The most commonly used powders include bronze, stainless steel, nickel and nickel-base alloys, titanium and aluminium. As mentioned above, while operating selflubricating bearing, it receives acting force all the times even through it is lubricated. Consequently, improvement self-lubricating bearing in reducing wear and has less friction coefficient by dispersion hardening make bearing has longevity.
2. Experimental procedures Premixed 90-10wt% of copper-tin powder and 99.9% pure aluminium powder were mixed and blended together in various ratio of added aluminium: 0wt%Al (no adding), 5wt% and 10wt%Al. The mixture was compacted into cylindrical shape (1.1 mm. diameter and 1-1.3 mm. height) under a pressure of 2000 kg. Weight, size of the sample was measure to calculate density before sintering. Sintering is in a batch type alumina tube furnace maintained at 830 C and 900 C for 5, 30, 45, 60 and 90 min under argon atmosphere. After sintering samples weight, size were measured. Density and porosity are measure by Archimedes method. The samples were phase identified by using X-ray Diffractometer. Microstructure was investigated by using optical microscope and scanning electron microscope.
3. Results and discussion Results will be discussed in two parts: result from sample sintered at 900 C and after heat treatment. 3.1 Sintering temperature at 900 C It was found that microstructure of different sintering time sample look similar. Fig.1 shows microstructure of 0wt%Al, 5wt% and 10wt%Al sample sintered at 900 C for 30 min, (a) (c) at center of the sample (d) (f) at edge of the sample. Pores at the center of the sample are quite round but pores at the edge of the sample are irregular, and with added aluminium the pores become more irregular.
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(a)
(b)
(c)
(d)
(e)
(f)
Fig.1 microstructure of 0wt%Al, 5wt% and 10wt%Al sample sintered at 900C for 30 min (a) (c) at the center of the sample (d) (f) at the edge of the sample
Fig.2 and 3 demonstrate the density and hardness of 0wt%Al (no adding), 5wt%Al and 10wt%Al samples sintered at 900C.
0% Al
5% Al
10% Al
9 8
Bulk Density (g/cm )
7 6 5 4 3 2 1 0 0 20 40 60 80 100
Sintering Time (min)
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Fig. 2 Effect of sintering time and amount of aluminium on the density of Cu-10wt%Sn samples sintered at 900 C.
0% Al 5% Al 10% Al STD
70 60
Hardness (HV 1kg)
50 40 30 20 10 0 0 20 40 60 80 100
Sintering Time (min)
Fig.3 Effect of sintering time and amount of aluminium on the hardness of Cu-10wt%Sn samples sintered at 900 C.
Density of no adding aluminium samples sintered at 900C for 30 min was the greatest which was 7.81 gcm-3, with minimum porosity of 9.53% and the maximum hardness was 54.4 HV. Density of 5wt%Al and 10wt%Al adding samples sintered at 900C for 30 min was greatest, which were 6.63 and 5.44 gcm-3 respectively. The porosity was 15.53% and 27.96% respectively. However the hardness was maximum at 51.30 and 37.90 HV when sintered at 900C for 5 min. Samples without addition of aluminium have higher hardness than the ones with aluminium for all sintering time. Effect of aluminium on the density of the samples is as following: the lager addition of aluminium, the greater is the reduction in density in all sintering time. It is lower than the reference samples from the K.Powder factory. Therefore porosity increases and hardness reduces when adding larger amount of aluminium in all sintering time. The same correlation as found in samples sintered at 830 C. When the samples have less density and more porosity, this can cause stress concentration at the edge of the pores. Stress concentration is one of the causes that make the sample have lower hardness. Two possible causes of pore occurrence are vaporization of aluminium and Kirkendall void. Vaporization of aluminium occurs because aluminium
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has higher vapor pressure at high temperature. Vapor pressure of pure aluminium obeys equation 1. [2]
log (P ) = 10.917 16211 T
Eq.1
P is a vapor pressure in Pascal and T is an absolute temperature. Vapor pressure at 900 C is 0.17 10-3 Pa. Atmospheric pressure is much larger than vapor pressure of pure aluminium at 900C therefore vapor pressure effect can be neglected. Weight loss after sintering of samples sintered at 900C for different sintering time is shown in Table 1. Sintering time (min) 5 30 45 60 90 0 wt%Al (g) 0.040 0.015 0.040 0.025 0.025 5 wt%Al (g) 0.030 0.055 0.035 0.065 0.050 10 wt%Al (g) 0.030 0.035 0.045 0.035 0.035
Table 1 Weight loss after sintering at 900C for different sintering time
Lubricant weight plus aluminium weight for 0wt%Al, 5wt%Al and 10wt%Al samples are 0.045 g, 0.375 g and 0.715 g respectively. It can be seen that weight loss of all samples is less than lubricant weight plus aluminium weight. Therefore the main cause of pore occurrence in samples is from Kirkendall effect which is diffusion phenomenon of two species with different diffusion coefficient. This causes void in the samples. In this case void caused from tin and aluminium diffusing into copper faster than the reverse. Long sintering time gives tin and aluminium more time to diffuse into copper and larger amount of pores were created. Fig 4 6 show XRD patterns of samples sintered at 900C for 30, 60 and 90 min.
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AlCu4
10wt% Al
Intensity (a.u.)
5wt% Al
0wt% Al
20 30 40
50
2 Theta (Deg)
Fig.4 XRD Pattern of samples sintered at 900C for 30 min
60 70
80
AlCu4
10wt% Al
Intensity (a.u.)
5wt% Al
0wt% Al
20 30 40
2 Theta (Deg)
50
60
70
80
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AlCu4 AlCu4
10wt% Al Intensity (a.u.)
5wt% Al
Cu 5.6Sn Cu 5.6Sn
Cu 5.6Sn
0wt% Al
20 30
40
50
60
70
80
2 Theta (Deg)
XRD pattern show that the main phase found in samples is solid solution of 10wt% tin in copper ( phase, JCPDS #44-1477) which can be found in all samples. Furthermore, phase (JCPDS #06-0621) which is solid solution of high tin content in copper (25 26.5 wt % tin) and intermetallic compound AlCu4 (JCPDS #28-0006) still present in 10wt%Al samples. Splitted peak also occur in the samples sintered at 900C for 90 min, this splitted peak is matched with Cu-5.6Sn JCPDS files (JCPDS #31-0487). Relative amount of phases is as following: the amount of phase in 10wt%Al samples sintered at 900C increases with sintering time and amount of phase in 10wt%Al samples sintered at 900C decreases with increasing sintering time. While amount of phase increase with sintering time, so are the vacancies occurring from diffusion of tin into copper. Therefore density and porosity trend are as aforementioned.
3.2 Results from heat treatment Fig 7 shows the microstructure of samples sintered at 900C for 30 min and heat treated at 750C for 60 min of 0wt%Al, 5wt% and 10wt%Al sample, (a) (c) at the center of the sample, (d) (f) at the edge of the sample.
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(a)
(b)
(c)
(d)
(e)
(f)
Fig 7 Microstructure of samples sintered at 900C for 30 min and heat treated at 750C for 60 min of 0wt%Al, 5wt% and 10wt%Al sample (a) (c) at the center of the sample (d) (f) at the edge of the sample.
From the microstructures it was found that pores at center and edge of the sample slightly increase when compare to the ones before heat treatment. Table 2 show the density, porosity and hardness of 0wt%Al (no adding), 5wt%Al and 10wt%Al samples sintered at 900C and heat treatment at 750C. Al amount (wt%) 0 5 10 Bulk Density (g/cm3) 7.38 6.43 5.26 % Porosity 15.70 19.66 29.97 Hardness (HV 1kg) 51.00 69.20 39.60
Table 2 Density, porosity and hardness of 0wt%Al (no adding), 5wt%Al and 10wt%Al samples sintered at 900C and heat treatment at 750C.
Comparing density and porosity before and after heat treatment, it was found that density after heat treatment slightly lower than before heat treatment so porosity after heat treatment is slightly higher than before heat treatment. Hardness after heat treatment of 0wt%Al is slightly lower than before heat treatment. However, the sample with added
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aluminium, 5wt%Al and 10wt%Al, increase 37% and 25% respectively. Fig.8 show XRD pattern of sample sintering at 900C for 30 min and heat treated at 750C for 60 min
AlCu
10wt% Al
AlCu AlCu
Intensity
5wt% Al
0wt% Al
20 30 40 50 60 70
80
2 Theta (Deg)
Fig.8 XRD Pattern of samples sintered at 900C for 30 min and heat treated at 750C for 60 min
According to XRD pattern of heat treated samples, it was found that the main phase existing in samples is solid solution of tin in copper ( phase), same as in samples before heat treatment, and phase can be found in all samples. Five weight percent samples contain both phase and slight amount of phase and AlCu4. Ten weight percent samples contain , phase and AlCu4. When consider relative amount of phases in heat treated samples, it was found that for no adding aluminium sample contains only phase. For added aluminum sample, 5wt%Al contains phase, as a new phase which was not found in the sample before heat treatment. Ten weight percent aluminum sample has no new phase after heat treatment. Therefore the cause of reduction of hardness of no adding aluminum sample (0wt%Al) is pores formation and coalescence. Although density of 5wt%Al sample is slightly reduced, but the hard new phase AlCu4 existing in the sample increases its hardness.
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4. Conclusions 1. The larger addition of aluminium, the greater reduction in density and hardness in all sintering conditions and they are lower than the reference samples from the factory. 2. Porosity increases and hardness is reduced when adding larger amount of aluminium in all sintering time. 3. The main cause of pore occurrence in samples is from Kirkendall effect. 4. Additional heat treatment at 750C for 60 min can increase hardness of 5wt%Al and 10wt%Al samples by 37% and 25% respectively.
5. Acknowledgement This project is financially supported by the Graduated School of Chulalongkorn University. The authors would like to thank K.POWDER METAL CO., LTD for providing premixed Cu-10wt%Sn powder.
6. References [1] ASM Powder Metallurgy Committee. 1993. ASM Handbook Volume 7 Powder Metallurgy. Fifth Printing. United State of America [2] David R. Lide (ed), CRC Handbook of Chemistry and Physics, 84th Edition. CRC Press.Boca Raton, Florida, 2003; Section 4, Properties of the Elements and Inorganic Compounds; Vapor Pressure of the Metallic Elements [3] P.Villars, A.Prince & H.Okamoto, ASM Handbook of Ternary Alloy Phases Diagrams Volume 4.
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Feasibility Study of Lard Oil and LPG as Fuels for Aluminum Crucible Furnace
Supakiat Supasin1, Sumpun Chaitep2, Saritporn Vittayapadung3, Lin Lin3
1
Graduate Student, Mechanical Engineering Department, Faculty of Engineering, Chiang Mai University, Chiang Mai, Thailand Tel: +6686 6570937 Fax: +6653 942062 Email: Supakiat_31@hotmail.com
PARA Laboratory, Mechanical Engineering Department, Faculty of Engineering, Chiang Mai University, Chiang Mai, Thailand Tel: +6653 942005 Fax: +6653 942062 Email: Svmpvn@gmail.com
School of Food & Biological Engineering, Jiangsu University, Zhenjiang, P.R. China Email: S_Vittayapadung@hotmail.com, Lin780530@hotmail.com
Abstract This research was to study the used of alternative fuel from animal easily found in Thailand. Generally, diesel oil would be used for metals melting processes. A new package of aluminum crucible furnace and burner was designed and built, lard oil was selected to be used in this research. This paper indicates the possibility of using lard oil in combination with liquefied petroleum gas instead of diesel oil in aluminum melting process. The experiment results found that overall thermal efficiency of the system was equal to 6.47%. Five kilograms of aluminum was melted in 34.02 minutes, with fuel consumption of lard oil at 0.0015 kg/s, combined with fuel consumption of liquefied petroleum gas at 0.0013 kg/s and total fuel cost for aluminum melting was 25.1 baht/kg. While, the overall thermal efficiency of crucible furnace using diesel oil was equal to 6.64% with 33.22 minutes of melting time. The used of diesel oil obtained fuel consumption of 0.0027 kg/s aluminum melting cost was to 37.5 baht/kg. Finally, a comparison of aluminum melting cost under different fuel was described using lard oil in aluminum melting process. It could be concluded that lard oil has all benefit and appropriated to be used as a main fuel in melting process over the conventional use of diesel oil. Keywords: Lard Oil; LPG; Aluminum Crucible Furnace; Overall Thermal Efficiency
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1. Introduction At present, the foundry process is widely used in modern industries. Several specialized furnaces are used to melt the metal. Furnaces are refractory lined vessels that contain the material to be melted and provide the energy to melt it. Furnace design is a complex process, and the design can be optimized based on multiple factors. [1-2] Furnaces in foundries can be any size and they are designed according to the type of metals that are to be melted. Also, furnaces must be designed around the fuel being used to produce the desired temperature. Electricity, fossil oil, gas and drying fuel are normally used in melting process [3-5]. Metal casting is a manufacturing process by which a liquid material is usually poured into a mold, which contains a hollow cavity of the desired shape, and then allowed to solidify [6]. Melting is performed in a furnace. Virgin material, external scrap, internal scrap, and alloying elements are used to charge the furnace. Virgin material refers to commercially pure forms of the primary metal used to form a particular alloy. The solidified part is also known as a casting, which is ejected or broken out of the mold to complete the process. Casting materials are usually metals or various cold setting materials that cure after mixing two or more components together [7-8]. Metal casting is most often used for making complex shapes that would be otherwise difficult or uneconomical to make by other methods. Generally, cast steel and nonferrous metal, such as, copper, brass and aluminum would be used in metal casting process [9]. Aluminum Crucible in foundry industry is using much of energy, especially in its production process [10]. It is generally known that the prices of diesel oil and gas fuel are daily increased. Diesel oil was usually used in aluminum melting process. The demand of high energy consumption was caused of high investment cost [11]. In the foundry process of some materials was also use a lot of energy consumption [12]. Therefore, it was interesting, if this process could be decreased the energy consumption. Due to, Thailand is agricultural country, plenty of animal husbandry is popularly practiced [13]. Animal fat is obtained from the tissues of mammals in the commercial processes of rendering or extracting. It consists predominantly of glyceride esters of fatty acids and contains no additions of free fatty acids. Chemical reaction of animal fat is shown in Figure 1 [14]. In actuality, the animal source is not specified or required to give the origin of slaughtered animals. However, Thailand can produce animal fat, especially, swine fat or lard oil which is enough to expect used instead of diesel oil in this research. Figure 2 show animal slaughtered (swine, cattle and buffalo) for consumption in Thailand (year 2008) [15].
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O CH - OH + 3R - C - OH CH2 - OH
[Glycerol] [Fatty Acid]
CH2 - OH
O CH2 - O - C - R O CH - O - C - R + 3H O 2 O CH2 - O - C - R
[Fat & Oil] [Water]
Figure 1. Chemical reaction of animal fat
8,000,000 7,000,000 6,000,000 Slaughter livestock Expected Slaughter livestock
N um ber
5,000,000 4,000,000 3,000,000 2,000,000 1,000,000 Cattle Buffalo Swine
Figure 2. Animal slaughtered in Thailand 2008.
From overall review, it was found that animal fat, especially, lard oil might be used instead of fossil fuel such as diesel oil. Consequently, lard oil was used as main fuel in this research [17]. The main objective of this research was to design and build the burner for aluminum crucible furnace using Liquefied Petroleum Gas (LPG) combine with lard oil as fuels in aluminum melting process. This would be the alternative way for energy saving and decreased the investment cost in foundry industry.
2. Lard Oil as Fuel The pig abdominal fat is one of low cost product and it can be produced as the lard oil fuel with quantity ratio of 90% by mass [16]. Lard oil is consisted chiefly of olein that is expressed from lard and used especially as a lubricant, cutting oil or illuminant. Its specification could say that similar to diesel oil. Table 1 show the comparative properties results between lard oil and diesel oil which was experimented in PARA laboratory, Faculty of Engineering, Chiang Mai University, Chiang Mai, Thailand [18].
Table 1 Property of Lard Oil and Diesel

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Properties of Fuels Heating Value (kJ/kg) Viscosity (cSt) (40oC) (90 C) Specific Gravity @ 25oC
o
Lard Oil* 41,688
Diesel Oil 42,500 2.2 5.3 -
44.077 11.491 0.85
* Lard oil measured from the experiment.
3. Theory Crucible Furnace system used some thermal theories to calculation as follows [19-21],
3.1 Heat quantity of fuel,
Qf
The heat quantity of fuel is calculated from the fuel combustion process which was determined from equation (1).

Q f = m f LHV
(1)
Where; Q f
= Fuel heat quantity; kW = Fuel mass flow rate; kg/s = Fuel low heating value; kJ/kg
mf
LHV
3.2 Air sensible heat, Q air The temperature of fuel fed in the combustion process was equal to outside temperature, in case of no fuel preheating. Air sensible heat could be calculated follow in equation (2)
Q air = mair C pair (Ta Tamb )

(2)
Where;
Q air
= Air Sensible heat; kW

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mair
= Air mass flow rate; kg/s = = = Specific heat capacity (Air); kJ/kgoC Air Temperature in Burner; oC Ambient Temperature; oC
C pair
Ta
Tamb
3.3 Heat loss through the furnace wall, Q wall The calculation of heat loss through the furnace wall consisting of refractory brick and steel sheet material was shown in equation (3).
Tw,in Tw,out In(r2 / r1 ) In(r3 / r1 + 2 kb L 2 ks L
Q wall =
(3)
Where;
Q wall
Tw,in
Heat loss through the furnace wall; kW
= Inside temperature of furnace wall; oC = Outside temperature of furnace wall; oC = Radius from center of furnace to inside refractory brick; mm = Radius from center of furnace to inside steel sheet; mm = Radius from center of furnace to outside steel sheet; mm = = = Thermal Conductivity of refractory brick; W/m-K Thermal Conductivity of steel sheet; W/m-K Height of furnace; mm
Tw,out r1 r2 r3
kb
ks
3.4 Exhaust gas heat loss, Q flue While, crucible furnace was operated, aluminum was melted by heat quantity of fuel. The heat loss of exhaust gas at the top of furnace that was released to the outside from a stack to environment could be calculated as follow in equation (4)
Q flue = m f C p , flue G (T flue Tamb )

(4)
Where;
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Q flue
= = = = = =
Heat loss in exhaust gas; kW Fuel mass flow rate; kg/s Specific heat capacity; kJ/kgoC Temperature of exhaust gas; oC Ambient Temperature; oC An exhaust gas quantity;
mf
C p , flue
T flue
Tamb
3.5 Heat transfer to aluminum material, Q m The heat quantity would be transferred to aluminum material in the crucible inside the furnace. This calculation could be determined by equation (5)
m C (T T ) mA LH Q m = A p , A melt start + tmelt 60 (tmelt ,end tmelt ) 60
(5)
Where;
Qm
mA
= =
Heat transfer to aluminum; kW Mass of aluminum in one batch; kg
C p, A
= Specific heat capacity of aluminum; kJ/kgoC = = = = = Melting point of aluminum; oC Initial temperature of aluminum; oC Latent heat; J/kg Initial melting time; min End of melting time; min
Tmelt
Tstart
LH
tmelt
tmelt ,end
3.6 Thermal efficiency of crucible furnace, furnace Thermal efficiency is a measure of the efficiency of converting a fuel to energy and useful work. It used for evaluated the performance of aluminum crucible furnace. Thermal efficiency of aluminum crucible furnace could be followed by equation (6)
furnace =
Qm
100
(6)
Q input
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Where;
furnace =
Thermal efficiency; % Quantity heat product; kW Quantity heat inlet; kW
Qm
= =
Qinput
4. Materials & Methods 4.1 Design and Construction This research was to design and construct crucible furnace system for aluminum melting process. The crucible furnace used materials which easily found in Thailand, it consisted of Refractory brick No.SK36, Steel sheet St.37, Refractory mortar No.70AM. In case of burner (See Figure 3), its components included of stainless steel (SUS-304) pipe 4 inch, Lard oil pipe used SUS-304 size 3/8 inch diameter, Venturi size 4 inch diameter and Heat buffer was modified from refractory brick No.C2. Figure 3 shows the components of burner which constructed in our laboratory. From figure 3, air inlet at position 1 to 3, in the other hand, LPG was also supplied from position 2 to 3. Position 3 was the combustion and burner to burn LPG and air inlet. Heat transferred from position 3 (660oC) to the venturi in position 4 and heat buffer transferred heat to lard oil which moved inside the SUS-304 stainless pipe.
N o. 1 2 3 4 5 6 7
D e s c rip tio n s A ir in le t L P G in le t L P G b u rn er V e n tu ri a n d la rd o il o u tle t H eat b u ffer H eat exchanger E x h a u s t o u tle t
Figure 3. Components of burner Lard oil viscosity was decreased and heated up while being moved to position 4. It was then forced feed and entrained with moving air to position 5. Finally, the droplet touched high temperature heat buffer. The flame oxidation was visible through out behind position 7.
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The crucible furnace with burner was constructed in this research as shown in figure 4.
Figure 4. Aluminum crucible furnace using liquefied petroleum gas and lard oil as fuel 4.2 Experimental Methodology The experiment of aluminum crucible furnace using petroleum gas and lard oil as fuel system for melting 5 kg/batch of aluminum was tested in PARA Laboratory, Faculty of Engineering, Chiang Mai University, Chiang Mai, Thailand.
5. Results & Discussions 5.1 Principle Burner Testing After finished burner construction, it was tested to determine the properties. Burner testing results were shown in Table 2.
Table 2 Burner tested properties Mass flow rate (kg/s) No Air 1 2 3 4 5 Lard LPG Output Temp. (oC) Combustion Efficiency (%) 96.76 74.10 72.36 88.80 97.32
0.042 0.0010 0.0001 1,027.0 0.050 0.0013 0.0001 1,076.0 0.055 0.0014 0.0001 1,051.0 0.061 0.0014 0.0001 0.061 0.0012 0.0001 965.3 853.4
The testing results of burner were found that the capacity of combustion burner which was designed and constructed could be used in aluminum crucible for melting process. Because burner provided the maximum temperature (1,076oC), was higher than melting point of
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aluminum (660oC). Figure 5 was the burner testing.
Figure 5. Burner testing in PARA Laboratory 5.2 Aluminum melting process using lard oil and LPG as fuel The results of aluminum melting process using lard oil and LPG as fuel exhibited the temperature inside furnace, air released temperature, crucible temperature and temperature of aluminum were related in this experiment. It was found that air flow rate representing 0.0302 kg/s, while, lard oil fuel flow rate and LPG fuel flow rate were 0.0015 kg/s and 0.0013 kg/s, approximately. The experiment was done till aluminum (solid) become aluminum (liquid). The result was shown in figure 6. Graph in figure 6 indicated that the trends of temperature lines were continuously increase. While, all aluminum in crucible was melted, it obtained the highest temperature of aluminum melting was 962.38oC and took 34.02 minutes melting time. Finally, molten aluminum was ready to be poured into the molds.
1200
1000
T em pera ture ( o C )
800
600 400
200 0 0 5 10 15 20
Temperature in Furnace Temperature Outlet Temperature Crucible Temperature Aluminum

25 30 35
Melting Time (Minute)
Figure 6. Aluminum temperatures in crucible furnace using LPG and lard oil as fuel
5.3 Aluminum melting process using diesel oil as fuel The results of aluminum melting process using diesel oil as fuel exhibited the temperature inside furnace, air released temperature, crucible temperature and temperature of aluminum were related in this experiment. It was found that air flow rate representing 0.030 kg/s, while, diesel oil fuel flow rate was 0.0026 kg/s. The result was shown in figure 7.
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1200 1000
T emperature ( C )
800 600 400 200 0 0 5 10 15 20 25 30 35
Temperature in Furnace Temperature Outlet Temperature Crucible Temperature Aluminum
Figure 7. Aluminum temperatures in crucible furnace using Diesel as fuel
Graph in figure 7 indicated that the trends of temperature lines were continuously increase. While, all aluminum in crucible was melted, it obtained the highest temperature of aluminum melting was 1,000oC and took 33.24 minute melting time consumption. Finally, molten aluminum was ready poured into the molds.
5.4 The comparison of aluminum temperatures between lard oil and Diesel oil in melting system. From item 4.2 and 4.3, the aluminum temperatures caparisoned between lard oil and diesel oil in melting of 4 kg aluminum. Graph in figure 8 showed the aluminum temperature using different fuels. The result shown in figure 8 was found that aluminum temperature using diesel oil was higher than lard oil in melting process, due to, high heating value of diesel oil was higher than lard oil. However, the results of these 2 fuels used did not much different. Burning temperature of lard oil as fuel was also enough to melt the aluminum.
1200
1000
Temperature (o C)
800
600
400
200
Furnace Diesel
0 0 5 10 15 20 25
Furnace Lard Oil

30 35
Figure 8. The aluminum temperature comparison using different fuels
Therefore, it was proved that lard oil with LPG as fuel in aluminum melting process could be used instead of diesel oil. This would be one of new choice to select and use alternative
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energy which easily found in Thailand, remunerated the fossil fuel.
6. Conclusions This research was to study the used of alternative fuel from animal easily found in Thailand. Generally, diesel oil would be used for metals melting processes. The new package of aluminum crucible furnace and burner were designed and built, lard oil was selected to use in this research. This paper indicates the possibility of using lard oil in combination with liquefied petroleum gas instead of diesel oil in aluminum melting process. The experiment results were found that overall thermal efficiency of the system was equal to 6.47%. Five kilograms of aluminum was melted in 34.02 minutes, with fuel consumption of lard oil at 0.0015 kg/s, combined with fuel consumption of liquefied petroleum gas at 0.0013 kg/s and aluminum melting cost was to 25.1 baht/kg. While, the overall thermal efficiency of crucible furnace using diesel oil was equal to 6.64% with 33.22 minutes of melting time process. The used of diesel oil obtained fuel consumption of 0.0027 kg/s aluminum melting cost was to 37.5 baht/kg. Finally, a comparison of aluminum melting cost under different fuel was described using lard oil in aluminum melting process. It could be concluded that lard oil has all benefit and appropriated to use as main fuel in melting process over the conventional use of diesel oil.
7. Acknowledgements The authors gratefully thank the financial supports from postgraduate thesis fund, Small Gas Turbine Development Research, Institute for Science and Technology Research and Development, PARA (Propulsion & Aerodynamics Research & Application) and FAME (Food & Agricultural Machinery Engineering) Laboratories and the department of Mechanical Engineering Faculty of Engineering Chiang Mai University, Thailand. And special thanks to the School of Food & Biological Engineering for this cooperative work.
8. References [1] B. Cabric, T. Pavlovic and A. Janicijevic, Regulation of the crystallization in a crucible Furnace, Journal of Crystal Growth, Vol. 20, 1998. pp 339-340. [2] H. Calisto, N. Martins and N. Afgan, Diagnostic system for boilers and furnaces using CFD and neural networks, Expert Systems with Application, Vol. 35, 2008. pp 17801787. [3] A.R. Khoei, I. Masters and D.T. Gethin, Design optimization of aluminum recycling
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process using Taguchi technique, Journal of Materials Processing Technology, 127, 2002. pp. 96-106. [4] V. Krivandin and B. Mrkov, Metallurgical Furnaces, Mir Publishers. Moscow. Russia, 1980. 509 pp. [5] Y.J. Zhang, P.V. Barr and T.R. Meadowcroft, Continuous Scrap Melting In a Short Rotary Furnace, Minerals Engineering, Vol. 21, 2008. pp 178-189. [6] L.J. Yang, The effect of casting temperature on the properties of squeeze cast aluminum and zinc alloys, Journal of Materials Processing Technology, 140, 2003. pp. 391-396. [7] O. Auchet, P. Riedinger, O. Malasse and C. Iung, First-principles simplified modeling of glass furnaces combustion chambers, Control Engineering Practice, 116, 2004. pp. 14431456. [8] P.M. Sobrinho, J.A. Carvalho, J.L. Silveira and P.M. Filho, Analysis of aluminum plates under heating in electrical and natural gas furnaces, Energy, Vol. 25, 2000. pp. 975-987. [9] A.R. Khoei, I. Masters and D.T. Gethin, Numerical modeling of the rotary furnace in aluminum recycling processes, Journal of Materials Processing Technology, 139, 2003. pp. 567-572. [10] M. Jackson, M.L. Pantoya and W. Gill, Characterization of a gas burner to simulate a propellant flame and evaluate aluminum particle combustion, Combustion and Flame, 153, 2008. pp. 58-70. [11] G.L Borman and K.W. Ragland, Combustion Engineering, WCB McGraw-Hill. Int., 1998. 613 pp. [12] Energy Information Administration (EIA), Official Energy Statistics from the U.S. Government, 2008. [Online] Available: http:// tonto.eia.doe.gov/oog/diesel.asp. [13] Department of Livestock Development, Livestock Infrastructure Information, Ministry of Agriculture and Cooperative of Thailand, 2007. [Online] Available:
http://www.dld.go.th/i /index.html [14] N. Rattanapanont, Food Chemistry, 1st edition, Odian Store, Bangkok, 2001. 487 pp. [15] Department of Livestock Development, Animal Statistics Ministry of Agriculture and Cooperative of Thailand, 2008. [Online] Available:
http://www.dld.go.th/jxbvict/stat_web /index _stat.html [16] U. Werner, U. Stohr and N. Hees, Biogas plants in animal husbandry, BAU-Biogas advisory unit, 1999. 153 pp. [17] S. Supasin and S. Chaitep, Lard as an Alternative Fuel Replacing Diesel Oil in Crucible Furnace, The 2nd Symposium on Engineering and Architecture for the Sustainable
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Development in the Greater Mekong Sub-Region, Luang Prabang, Laos, 2008. pp 91-94. [18] S. Supasin, S. Chaitep and N. Vorayos, Design of Burner for Aluminum Crucible Furnace using Liquefied Petroleum Gas (LPG) and Land Oil as Fuels, The 15th TriUniversity International Joint Seminar and Symposium, Zhenjiang, P.R. China, 2008. pp 194-197. [19] J. Gosse, Technical Guide to Thermal Processes, Cambridge University: England, 1986. 227 pp. [20] K.V. Mitzlaff, Engines for Biogas Theory, Modification, Economic, Operation, Federal Republic of Germany, 1988. 133 pp. [21] S. Sarannit, Heat Transfer, Technology Promotion Association (Thailand-Japan), 1st edition, 2002. 467pp.
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Development of an aluminum semi-solid extrusion process

T. Rattanochaikula, S. Janudoma, N. Memongkolb ,J. Wannasina*
a
Department of Mining and Materials Engineering, Faculty of Engineering, Prince of Songkla University, Hat Yai, Sonkhla 90112, Thailand.
b
Department of Industrial Engineering, Faculty of Engineering, Prince of Songkla University, Hat Yai, Sonkhla 90112, Thailand. *Corresponding Author: jessada.w@psu.ac.th
Abstract An aluminum extrusion process is mainly used to fabricate long tubes, beams and rods for various applications. However, this process has a high production cost due to the high investment cost of high-pressure machinery. The objective of this work is to develop a new extrusion process using a semi-solid metal forming technology. In this study, a laboratory extrusion system was used to fabricate aluminum rods with the diameter of 12 mm. The semi-solid metal process used in this study is the Gas Induced Semi-Solid (GISS) technique. To study the feasibility of the GISS extrusion process, the effects of extrusion parameters such as plunger speed and solid fraction on the extrudability and microstructure of extruded samples were investigated. The results show that the plunger speed and solid fraction of the semi-solid metal need to be carefully controlled to produced complete extruded parts.
Key words: Aluminum alloys; Aluminum extrusion; Semi-Solid Metal; Extrusion process; Microstructure; Gas Induced Semi-Solid (GISS)
1. Introduction Extrusion is one of various forming processes that is used to produce long, straight metal products with constant cross section, such as bars, solid and hollow sections, tubes and wires [1]. In the process, a billet is heated and forced through a die orifice. The products from this extrusion process are near net shape and long. However, the extrusion process
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requires a high-pressure machine to force the metal in the solid state. In addition, defects such as surface defect and piping can be present in the products of an extrusion process [1]. Semi-solid rheo-extrusion is a new extrusion process that has several advantages such as low extrusion force, high fluidity of materials, and low friction force between the die and the materials [2]. In a rheo-extrusion process, the metal alloy is melted in a furnace and then extruded at a temperature between the solidus and liquidus temperature of the metal alloy. The slurry is forced through a die orifice to form a desired part. Several previous studies have been reported regarding the behaviors of the rheoextrusion process. However, no complete research in the rheo-extrusion process has been published [3-5]. To apply the rheo-extrusion process in the production of commercial parts, it is important to conduct further studies. This research paper reports a preliminary research and development work of a new rheo-extrusion process using the Gas Induced Semi-Solid (GISS) technique. In this study, the effects of the plunger speeds and solid fractions on the extrudability of an aluminum A356 alloy were investigated.
2. Materials and Experimental Procedure The raw material used in this work is aluminum A356 alloy. The chemical composition of the alloy is shown in Table 1.
Table1. Chemical composition of aluminum A356 alloy Element Si Fe 0.42 Cu 0.05 Mn 0.04 Mg 0.42 Zn 0.01 Ti 0.10 Al Bal.
Weight% 6.9
Preparation of semi-solid slurry: The aluminum A356 alloy was melted in an electric furnace at the temperature of about 650C. Approximately 300 grams of the molten aluminum was taken from the crucible by a ladle. When the temperature of the molten aluminum was about 620C, a graphite diffuser was immersed to induce nitrogen gas for 5 seconds. A semi-solid slurry with the solid fraction of about 10% was then obtained. A schematic drawing of the GISS technique and the GISS machine is shown in Figure 1.
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(a)
(b)
Figure 1: (a) Schematic drawing of the GISS technique [6] and (b) the GISS machine to prepare semi-solid slurry Rheo-extrusion test: The semi-solid slurry from the GISS machine was then poured into a shot sleeve with the inner diameter of 40 mm. The shot sleeve was preheated to about 350C-400C. Next, the slurry was forced by a plunger at various speeds of 2, 4, and 6 cm/s through a die, a graphite support and a water-cooled tube. The inner diameter of the die was 12 mm. The schematic drawing of this rheo-extrusion process is shown in Figure 2. The holding time of the slurry in the shot sleeve, 0 second and 5 seconds at each plunger speed, was also studied in this work. Figure 3 shows the extrusion die and the laboratory-scale extrusion machine. This machine has a 20-ton capacity with a hydraulic system.
Figure 2: The schematic drawing of this extrusion process.
Figure 3: The extrusion die and laboratory-scale machine used in this study.
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Results analysis methods The extruded samples were analyzed by three criteria to determine the extrudability. The methods are briefly described as follow: Length of the samples:, the length of the samples was measured after the extrusion test. In this work, the criterion for the required length was 15 cm. shorter samples then the criterions were rejected. Surface quality: The surface of the samples was also examined. Samples with smooth surfaces in all the area would pass the requirement. Microstructure uniformity: the microstructure of samples was observed using an optical microscope. The samples were cut and obtained from two positions as shown in Figure 4. The samples were then prepared for metallographic analysis using the standard grinding, polishing and etching procedure. Good extruded parts should have uniform microstructure throughout the length.
1 inch
1 inch
Sample
Figure 4: The sampling position.
3. Results and Discussion The representative extruded samples from the experiments are given in Figure 5. The results show that faster plunger speed and lower holding time yield longer samples. Only the sample with a low plunger speed of 2 cm/s and a longer holding time of 5 s did not pass the length criteria. (see Table 2.) The results suggest that conducting the rheo-extrusion process with a high speed and with the low-solid-fraction slurry (no holding time) gives the longest length as expected since the slurry can flow easier and faster.
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Table 2. The semi-solid extrudability of A356 Al-alloy 0s 5s
length Surface length Surface 2 cm/s 4 cm/s 6 cm/s x x x x x
24cm 6cm/s 23cm 4cm/s 14cm 2cm/s
(a)
35cm 6cm/s 30cm 4cm/s 27cm 2cm/s
(b) Figure 5: The samples from GISS extrusion at (a) each plunger speed and 5 seconds of holding time and (b) each plunger speed and 5 seconds of holding time.
(a)
(b)
Figure 6: The surface finished of samples of (a) 4cm/s of plunger speed and holding time is 5 seconds and (b) 4cm/s of plunger speed and no holding time.
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However, when the surfaces of the samples were examined, the samples produced by fast speed and at a low solid fraction have surface defect as shown in Figure 6(b). Only the samples produced by lower speed (2-4 cm/s) and at a higher solid fraction pass the surface quality requirement. The fast flow speed of the slurry may cause turbulent flow causing the surface defect. By increasing the viscosity of the slurry through increasing the solid fraction, the slurry will have laminar flow at the same flow speed. From these results, only samples produced by the conditions of 4 cm/s plunger speed and holding time of 5 seconds pass the requirements of length and surface quality.
(a) Middle
(b) Edge Figure 7: The representative microstructures of the cross section of the samples
For all the samples, the microstructures at the edge and the middle are similar. Figure 7 shows representative microstructures at the edge and the middle of the samples. The micrographs show that the solid particles are concentrated near the center of the channel
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during the flow. Representative microstructures of the samples at the tip and the base of the rods at various plunger speeds and holding times are given in Figure 8-9.
At tip of samples
At base of samples
Plunger speed is 2 cm/s and no holding time
Plunger speed is 4 cm/s and no holding time
Plunger speed is 6 cm/s and no holding time Figure 8: The microstructure of each sample that no holding time.
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At tip of samples
At base of samples
Plunger speed is 2 cm/s and 5 seconds of holding time
Plunger speed is 4 cm/s and 5 seconds of holding time
Plunger speed is 6 cm/s and 5 seconds of holding time Figure 9: The microstructure of each sample that have 5 seconds of holding time. In general, the amount and distribution of the primary phase in all the samples are quite uniform. However, the eutectic structures in the samples at the tip and the base of the rods are different. The eutectic phase at the tip has coarse structure, as shown in Figure 10. Fine eutectic structure is observed at the base of the rod. The results show that the metals near the tip have longer solidification time so that the eutectic structure can grow larger. To improve this, a better cooling system should be applied in the rheo-extrusion system.
Coarse Eutectic
Fine Eutectic
(a) Tip
(b) Base
Fig 10: The different eutectic structure at each position.
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4. Conclusions From this study, the following conclusions can be drawn: 1. The extrusion behavior of an aluminum A356 alloy using the GISS technique is influenced by the plunger speed and the solid fraction of the slurry in the shot sleeve. 2. The higher solid fraction of the slurry helps reduce the surface defects of extruded parts. 3. The non-uniformity of the eutectic microstructure is caused by inefficient cooling of the extruded samples. This problem can be improved by adding a better cooling system along the die. 4. This preliminary study gives important information for the development at the rhoextrusion machine using the GISS technique in the future.
5. Acknowledgements The authors gratefully thank the Department of Mining and Materials Engineering, Faculty of Engineering, Price of Songkla University for financial support and facilities. We also thank Miss Rungsinee Canyook for the metallographic preparations and the Innovative Metal Technology (IMT) team for all the kind supports.
6. References 1. Pearson, C. and Parkins, R. 1960. The extrusion of metal. London : CHAPMAN & HALL LTD.
2.
Gerhard, H. and Reiner, K. 2004. Thixoforming. WILEY-VCH Verlag GmbH & Co. KGaA.
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B.S. Lee., D.H. Joo., M.H. Kim. 2005. Extrusion behavior of Al-Cu alloys in the semisolid state, Materials Science and Engineering A402 (2005) 170-176
4.
Zhang, L.N., Wang, S.Q., Zhu, M.F., Wang, N. and Wang S.D. 2003. The extrusion behaviour of Zn-20% Al alloy in the semi-solid state, Journal of Materials Processing Technology Vols. 44: 91-98.
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5.
Jae-Ho Hwang, Dae-Cheol Ko, Gyu-Sik Min, Byung-Min Kim and Jae-Chan Choi. Finite element simulation and experiment for extrusion of semi-solid Al 2024, International Journal of Machine Tools and Manufacture Vols. 10: 1311-1328.
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Wannasin, J. and Thanabumrungul, S. 2008. Development of a semi-solid metal processing technique for aluminum casting Technol., 30(2): 215-220. applications. Songklanakarin J. Sci.
7.
Wannasin, J., Junudom, S., Rattanochaikul, T. and
Flemings, MC. 2080.
Development of the Gas Induce Semi-Solid Metal Process for Aluminum Die Casting Applications, Solid State Phenomena Vols. 141-143:97-102.
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The Preparation of Silicon Nitride by Silicon Source from Rice Husk Ash
S. Rattanaveeranon1*and D. Bhongsuwan2 Department of General Education (Physics), Rajamangala University of Technology Rattanakosin, Salaya, Phuttamontol, 73170, Thailand, Tel: +662-8894585-7 ext.2920 Fax +662-8894585 ext.2920 2 Materials Science Program, Faculty of Science, Prince of Songkla University, Hat yai, Songkhla 90110, Thailand, Tel: +6674-288396 Fax: +66-74218701
* 1
Corresponding Author E-Mail : santi.r@rmutr.ac.th
Abstract: This study aims at the preparation of silicon nitride powder from rice husk silica by chemical and thermal degradation. The composition of silica powders were mixed with carbon powders by ratio 20 : 12 wt% and calcined at temperature 1400C at the rate of 5 Cmin-1 under N2 atmosphere of 1 dm3.min-1.The soaking temperature was maintained for a period of 4, 5 and 6 hours, respectively. The XRD analysis shows the presence of cristobalite at firing temperature 1400C and soaking time of 4 hours. The appropriate temperature for silicon nitride formation is at 1400C with the soaking time of 6 hours. The scanning electron micrograph shows the surface morphology of silicon nitride phase consisting of fibers and/or whiskers. Introduction Silicon nitride (Si3N4) has been widely used to fabricate cutting tools and high-temperature structural applications due to its excellent mechanical, physical and chemical properties. The Si3N4 ceramics with a tailored microstructure are promising high performance materials because of such unique properties as light weight, good strain tolerance, damage tolerance and thermal shock resistance. Traditionally, the Si3N4 ceramics have been used as hot gas filters, high-temperature separation membranes, and catalyst supports. Recently porous Si3N4 ceramic is also attractive in electromagnetic wave penetrating materials, as a strategy to reduce dielectric constant and loss. Materials and Methods
Starting material, by using the rice husk of 65 g. was reacted by 3 M of hydrochloric acid concentres and then filtered the sample by plastics grate, then washed the sample with pure
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water several times, finally washed the sample with distilled water, dried the sample at 100
C with the soaking for 2 hours and then brunt the sample at 850 C with the soaking for 3
hours (increasing temperature rate = 20 Cmin-1). It was obtained the pure silica powder (SiO2) (pure silica over than 95 wt.%,), The sample was prepared by abovementione to mix with activated carbon (pure 99.99 wt.%, 0.52 m).The samples were prepared to mix by ration 20 : 12 wt.% (SiO2 : C).The mixtures were ball-milled for 24 h using ceramic balls. Absolute ethanol was used as the milling media.The resultant slurry was dried to obtain an agglomerate-free powder mixture to dry box at 100 C for at least 3 hours to ensure that the powders were completely free of alcohol. The dried powders were then sieved to 60mesh.The sample was calcined at 1400 C with varying the period of calcined time for 4, 5 and 6 hours, respectively.X-ray diffractometry (XRD) analysis was conducted to examine the phases in the obtained silicon nitride ceramics and X-ray fluorescence(XRF) was analyzed the chemical compounds of rice husk ash. The laser particle sizing analyzer (LPSA) was measured an average particle. The morphologies of combustion products were studied by using scanning electron microscopy (SEM).
Results Table1. shows the analysis by using XRF technique using for analyzing chemical compounds of rice husk ash (RHA).The main chemical compounds of this product is silica and there is amorphous structure.(more than 99 wt.%) Furthermore, there is a trace element such as alumina and calcium oxide of only 0.65. The hydrochloric concentrate of 3 M is enough to remove all of the impurity in rice husk ash. Table 1: Show that the chemical compounds of rice husk ash which calcined at 850C for 3 hours.
Compounds Silica (SiO2) Alumina (Al2O3) Calcium Oxide (CaO) Others
Concentrate (%) 99.35 0.23 0.41 0.01
Fig1. Shows the distribution of particle size of silica powder.
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The distribution of particle size of silica powder consists of 3 types. First, the particle size is less than 10 % which is 1.66 m. Second, the mean particle size of silica powder is 83.04 m. Third, the particle size is more than 90 % which is 326.08 m, respectively.(the samples were ball milled for 12 hours)
50 %
Volume (%)
10 %
0 10 -2 10-1 10 0 10 1 10 2
100 %
10 3 10 4
Particle size (m)
Fig.1 The particle size of silicon oxide was milled for 12 hours.
Fig.2 shows the XRD pattern of silicon nitride calcined at temperature 1400 C at the rate of 5 C/min in nitrogen atmosphere of 1 dm3min-1 soaked for 4 hours. There is no silicon nitride in the sample but there is only cristobalite-silica structure Fig.2(a). When the sample was calcined for 5 hours , it began to have silicon nitride and silicon oxide nitride Fig.2(b). Furthermore, there is unreated silica which betides the silica-cristobalite only. The sample was calcined for 6 hours, there was only the silicon nitride Fig.2(c) and there were two forms ; -silicon nitride and -silicon nitride mixing in the sample.
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2 2
2- Cristobalite low
(a)
1-Si3N4 3-Si2N2O2
(b)
1 1 1
1-Si3N4
(c)
Fig.2 The XRD pattern of SiO2+C was calcined in pure nitrogen gas 99.9% with the soaking time for 4 hours (a), 5 hours (b) and 6 hours(c)
Fig.3 The SEM morphology of SiO2+C compound was calcined in pure nitrogen gas 99.9% with the soaking time for 4 hours
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Fig.4 The SEM morphology of SiO2+C compoundswas calcined in pure nitrogen gas 99.9% withthe soaking time for 5 hours.
Fig.5 The SEM morphology of SiO2+C compoundswas calcined in pure nitrogen gas 99.9% withthe soaking time for 6 hours. Discussion The hydrochloric concentrate of 3 M is enough to remove all the impurity in rice husk ash. These impurities were easily leaching by concentrate acid and then washed the sample with distilled water several times. After that the rice husk was calcined at 850 C (carbon was thermal decomposed at 550 C) Finally, the pure silica rice husk was obtained. From the XRD pattern, it shows if the silica rice husk ash mixed with carbon at the ratio of 20 : 12 wt.% which is calcined at 1400 C for 4 hours, silicon nitride is not obtained. But there is a form of silicon nitride and silicon oxide nitride impure agglutinated in the sample. If the sample is calcined for 6 hours, there is only the silicon nitride with two forms; -silicon nitride and -silicon nitride mixing in the sample. The calcined time of 6 hours was the optimal condition for preparing the silicon nitride.
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The SEM morphology Fig.3-5 at 5,000 magnifications, it shows that the surfaces of calcined sample of 4 hours became porous which is weaving into a network across the sample but in some parts there were small sphere affiliated within a long stripe. When increasing the calcined time upto 5 hours, the there was less porous in the material of the surface then it was conglomerated into a clump and there was a little bit fiber. But if we increased the calcined time up to 6 hours there was the least porous in the material and there was the whisker which was orthogonal with the surface of sample Conclusions
The hydrochloric concentrate of 3M can well remove the impurities in rice husk and results in the purity of product more than 99 %. The silicon nitride was formed when calcined at temperature of 1400 C more than 6 hours continuously which results in silicon nitride and -silicon nitride mixing in the sample. The porosity of samples were decrease when the calcined temperature was increase.
References
[1] Dianying C., Baolin Z., Hanrui Z. and Wenlan L. (2003) Combustion synthesis of network silicon nitride porous ceramics, Cera Inter 29 pp. 363364 [2] Grechikhin L. I. and Golubtsova E. S.(2004) : Silicon-Nitride-Based Nanoceramic Materials, Inor. Mater., 41, pp. 140-127 [3] Lee J.S., Muna J. H., Hanb B. D.,Kimb H. D., Shin B.C.,and Kim S.(2004) Effect of raw-Si particle size on the properties of sintered reaction-bonded silicon nitride Cera Inter., 30 pp. 965976
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MetallurgicalResearchforThailandDevelopment 2627October2009 CenturyParkHotel,Bangkok,Thailand

SahaviriyaSteelIndustriesPublicCo.,Ltd ThaiParkerizingCo.,Ltd BoonRawdBreweryCo.,Ltd. ThaiNipponSteelEngineering&ConstructionCorp.,Ltd. AdvancePinnacleTechnologiesPteLtd. DKSHLtd. CouncilofEngineers,Thailand

Table 1 Welding conditions Parameter Electrode Types (AWS) Unit

350 350 4 145 26 160 1.41

350 12 1.2 230 25 300 1.15

350 12 1.2 230 25 300 1.15

l/min mm. A V mm/min KJ/mm

Fig.3. Volume fraction of microstructures in different processes.

School of Metallurgical Engineering, Institute of Engineering,

Suranaree University of Technology, Nakhon Ratchasima, 30000 Thailand

V [1]. Seebeck coefficient or thermoelectric power is T 0 T

d 2E and are Planks dk 2

Figure 1: Diagram of Seebeck coefficient measurement apparatus

Results and discussion

Figure 3: X-ray diffraction pattern of as received sample and quenched samples

Figure 4: [110] peak of as received sample and quenched samples

Keywords Atmospheric Corrosion, ACM sensor, Carbon steel

Table 1. Locations of exposure test sties

SattahipNavyDockyard,Chonburi GulfofThailand Onthegroundnearbythe

runwayandindustrial district Ontherooftopofa7story

(a) Urban sheltered environment

(b) Airport and urban outdoor environment

250 Calculated CR [g/ m / y] 200 150 100 50 0 0 50 100 150

Figure 3 Calculated values compared to the actual values

4.0 M H2SO4; 85C followed by HNO3+HF; 45 C

Roughness (Rq) = 3.29 m Remaining oxide level 2

Roughness (Rq) = 3.30 m Remaining oxide level 0

4.0 M HCl; 85C

4.0 M HCl (Electrolytic); 85C

Roughness (Rq) = 3.34 m Remaining oxide level 3

Roughness (Rq) = 3.51 m Remaining oxide level 3

4.0 M H2SO4; 85C

4.0 M HCL; 85C

Roughness (Rq) = 3.81 m Remaining oxide level 3

Roughness (Rq) = 3.15 m Remaining oxide level 3

4.0 M H2SO4; 85C followed by HNO3+HF; 45 C

4.0 M HCl; 85C followed by HNO3+HF; 45 C

Roughness (Rq) = 3.29 m Remaining oxide level 3

Roughness (Rq) = 3.34 m Remaining oxide level 3

4.0 M H2SO4 (Electrolic); 85C followed by HNO3+HF; 45 C

4.0 M HCl; 60C followed by HNO3+HF; 45 C

Roughness (Rq) = 3.30 m Remaining oxide level 0

Roughness (Rq) = 3.24 m Remaining oxide level 3

4.0 M HCl+10g/L H2O2; 60C followed by HNO3+HF; 45 C

d 4.0 M HCl+10g/L H2O2; 60C

Roughness (Rq) = 2.92 m Remaining oxide level 0

Roughness (Rq) = 2.95 m Remaining oxide level 0

Fig.1 Showing the friction stir welding

Fig.2 showing two different tool pin profiles

3. Results and discussion

(a) The temperature of cylindrical pin

(b) The temperature of quare pin

(b) 120 mm/min

(e) 120 mm/min

(c) 160 mm/min

(f) 160 mm/min

Fig. 5 showing the photos of weld surface appearance

(b) 120 mm/min

(e) 120 mm/min

(c) 160 mm/min

(f) 160 mm/min

3.4 Microstructure of joint

(a) Base metal of SSM A356 Al alloy