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Interrupted Boriding of Medium-Carbon Steels

P. GOPALAKRISHNAN, P. SHANKAR, M. PALANIAPPA, and S.S. RAMAKRISHNAN The results of an extensive study on the microstructure, microhardness, corrosion, and tensile properties of continuously borided and interrupted borided specimens of medium-carbon steel are compared. Carbon repartitioning away from the surface is one of the principal modes to accommodate the high strains introduced on boron diffusion into the case. However, this is a kinetically constrained process and is more predominant on interrupted boriding. The effect of such a carbon redistribution is to result in microstructural modifications including (1) blunting of boride needle tips, (2) precipitation of nearly spherical and fine borocarbides, and (3) enhanced carbon segregation at the boride needle/ steel matrix interface on interrupted boriding. The mechanisms aiding the change in the morphology of the boride needles are discussed. The improvements in the mechanical and corrosion properties of the interrupted borided specimens over continuously borided specimens are described.

I. INTRODUCTION

THE surfaces of engineering components are subjected to higher stresses and greater fatigue, abrasion, and corrosive damages than the interior. Therefore, more than 90 pct of the service failures of engineering components initiate at, or near, the surface. Surface modification techniques are employed to improve the resistance to failure by producing a hard and wear-resistant case around a soft and tough core. Two major classes of treatments available for enhancing the surface properties are thermal and thermochemical. Thermal treatments, such as flame and induction hardening, modify the microstructure without modifying the surface chemistry, whereas in thermochemical methods, the surface chemistry is altered. Carburizing and nitriding are well known thermochemical methods.[1] Boriding or boronizing is a recent process, which is analogous to carburizing and nitriding. Boriding can develop surface hardness in the range of 1500 to 2000 HV, as compared to a hardness in the range of 600 to 1100 HV for nitriding, 700 to 850 HV for carburizing, and 950 to 1100 HV for chromium plating. Borided layers provide a wear resistance comparable to that of sintered carbides. The wear resistance of cold-working tools is increased by about 10 times and that of hot-working tools and dies by about 3 times as a result of boriding.[2] If the process has been performed properly and the right material and layer thickness have been chosen, boriding can extend the service life of engineering components beyond that imparted by traditional methods like carburizing or nitriding.[3,4] Various processes adopted for boriding include pack boriding, molten salt boriding, electrolytic boriding, gas boriding, vacuum boriding, etc. In pack boriding, the sample is cleaned and kept surrounded by solid mixtures consisting
P. GOPALAKRISHNAN, Assistant Professor, Department of Metallurgical Engineering, and S.S. RAMAKRISHNAN, Dean, School of Metallurgy and Materials, and Professor, Department of Metallurgical Engineering, are with PSG College of Technology, Coimbatore 641 004, India. P. SHANKAR, Scientist, is with the Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, India. M. PALANIAPPA, formerly ME Student, Department of Metallurgical Engineering, PSG College of Technology, is Doctoral Scholar, Indian Institute of Technology, Madras 600036, India. Manuscript submitted September 25, 2000.
METALLURGICAL AND MATERIALS TRANSACTIONS A

of boron carbide and borax mixtures.[5,6] Alternatively, boron carbide or amorphous boron has been used as the boron source, along with diluents such as silicon carbide or alumina or graphite and activators like KBF4 or NaF in the boriding mixtures.[4,6,810] Ferroboron can be considered as a boron source instead of boron carbide. However, it is reported that the commercial grades of ferroboron contain impurities like Si and Al; therefore, the use of this material leads to a degenerate layer. However, special-quality ferroboron can be used to get a good-quality boride case, according to the classical review book by Von Matuschka,[11] which is a comprehensive, general, and theoretical compendium on boriding. The molten salt boriding process is usually performed using anhydrous borax, mixed with reducing agents like boron carbide, silicon carbide, or silico-calcium.[12] Amorphous boron is stated to be better than boron carbide, since it produces less slurry.[13] Electrolytic boriding is carried out in inert atmospheres like argon, using borax-based melts at about 1173 K at a current density of about 0.15 to 0.25 A/ cm2.[14,15,16] Electrolytic boriding produces thicker coatings in relatively shorter times compared to molten salt or pack boriding processes.[16] There are many other techniques for boriding, e.g., gas boriding, vacuum boriding, plasma boriding, and thermal spraying of powders.[2,12,17] Out of all these techniques, pack and molten salt (electroless) processes are technologically simpler and more economical compared to other boriding processes. During boriding of plain-carbon steels, needle-like FeB and Fe2B phases are formed. When the boron potential is low, Fe2B phase alone forms in the case. At higher potentials of boron, FeB phase also forms along with Fe2B. The Fe2B phase forms adjacent to the core and the FeB phase forms near the surface.[4,10,12,18] It is reported that FeB19 phase also forms,[19] very rarely, when the boron potential is very high. A single-phase structure is desirable.[6] Fe2B is preferred to FeB,[10,20,21] since FeB is very hard and brittle and has a coefficient of thermal expansion that differs from the matrix by a factor of 3 and that causes spalling during cooling.[22] Although boriding of plain-carbon steels improves the wear, abrasion, fatigue, tensile, corrosion, corrosion-fatigue, and oxidation properties,[1,5,6,8,13,14,23,24] one serious drawback is the brittleness of the case.[6,23] Several methods have been attempted to solve this problem. They include (1) partial
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Fig. 2Interrupted boriding cycle.

Fig. 1Pack boriding setup.

deboriding of the saturated layer,[6] (2) the addition of copper to the borided layer,[6] (3) multicomponent diffusion impregnation of iron with elements like silicon, aluminium, etc., along with boron,[25] (4) superplastic boronizing, which produces a nonacicular structure with eqiaxed grains of the borides, thereby reducing brittleness,[26] and (5) laser surface modification of borided surfaces.[27,28,29] The objectives of the present study are (1) to develop low-cost boriding processes using low-cost and easily available raw materials, (2) to optimize the process parameters to get only Fe2B phase, resulting in better toughness, and (3) to improve the microstructural morphology and, thereby, increase the toughness and ductility of the boride layer by an interrupted thermocyclic boriding process. II. EXPERIMENTAL PROCEDURE In this study, boriding was performed using pack processes and molten salt (electroless) processes. The medium-carbon steel (0.45 pct C, 0.2 pct Si, 0.7 pct Mn, 0.05 pct S, and 0.05 pct P) specimens were ground with a rough emery paper to remove surface oxides. They were subsequently cleaned in a 50 pct aqueous solution of HCl and dried. A. Boriding Methods 1. Pack boriding process Initially, boron carbidebased powders were employed to develop the boride layer. Subsequently, ferroboron-based powders were also used to get a boride layer. Fine powders of the mixture were taken in a stainless steel container. The medium-carbon steel [EN8] sample of 10 mm in diameter and 10 mm in length was placed inside the box in such a way that the sample was uniformly surrounded by an approximately 15-mm-thick boriding mixture on all sides. The box was tightly closed, and the gap between the lid and the box was sealed with fireclay. The box was placed in a crucible (clay-graphite) surrounded by silica sand, as shown in Figure 1. 2. Molten salt (electroless) process Anhydrous borax and boric acid were melted in a muffle furnace, and the melt was reduced by stoichiometric amounts of ferrosilicon magnesium powder; 10 pct NaF was added along with the reducer to activate the melt.
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Fig. 3Tension test sample.

B. Thermal Treatment 1. Continuous process The assembly shown in Figure 1 was loaded in the furnace at around 1073 K, and it was further heated to the boriding temperature (1223 K). When the temperature reached 1223 K, boriding was performed continuously for 4 hours. After 4 hours, the crucible was removed from the furnace and allowed to cool in still air. In the case of the molten salt process, the sample to be borided was kept in the boriding melt and boriding was carried out at 1223 K for 4 hours continuously. After 4 hours, the sample was removed from the melt and allowed to cool in air. 2. Interrupted process In interrupted boriding process, after every hour of boriding, the crucible (with the stainless steel box containing the boriding mix and sample) was removed from the furnace and allowed to cool in still air. During cooling, a thermocouple was inserted in the sand so as to touch the stainless steel box. When the temperature was about 873 K, the crucible was again loaded into the furnace at 1223 K. Boriding was done for 1 hour at 1223 K, and the sample was cooled again to about 873 K. This procedure was repeated four times. The thermal cycle is shown in Figure 2. After the interrupted boriding process (four steps of 1 hour each), the crucible was removed from the furnace and kept at 873 K for 1 hour in a separate furnace. It was then cooled in air to room temperature. In the case of molten salt boriding, the sample was removed from the melt after every hour of boriding, cooled for 5 minutes in air, and again placed in the melt. The total boriding time was 4 hours. After this boriding treatment, the sample was heated for 1 hour at 873 K and then cooled in air. Two sets of specimens, one for metallography and microhardness work (10-mm diameter and 10-mm long) and the other for tension tests (5-mm diameter and 25-mm gauge length, as shown in Figure 3) were borided, separately.
METALLURGICAL AND MATERIALS TRANSACTIONS A

C. Microscopic Observations One flat end of the borided specimens was ground gently to remove the boride layer. Then, the samples were mounted in cold mounting material and prepared for metallographic study using various grades of emery papers. Final polishing was performed using diamond paste, and etching was carried out using equal quantities of nital and picral. The microstructure of the borided samples was studied and photographed using a Nikon-Epiphot optical metallograph. The metallographially polished specimens, as well as the fractured surfaces of the tension test specimens, were also observed using a JEOL* JSM T100 scanning electron microscope at
*JEOL is a trademark of Japan Electron Optics Ltd., Tokyo.

Fig. 4Schematic arrangement of Falex tester for evaluating scuffing resistance of materials. (a) Key components of instrument. (b) Exploded view showing arrangement of V-blocks and rotating journal.

suitable magnifications. D. Analysis by X-ray Diffraction Specimens borided by the various processes were analyzed using a PHILIPS* X-ray diffractometer with copper
*PHILIPS is a trademark of Philips Electronic Instruments Corp., Mahwah, NJ.

K radiation, X-ray diffraction and the (XRD) results were compared. E. Microhardness Measurements Microhardness measurements were carried out at 50 g load using a Mitutoyo microhardness tester. The cross section hardness profiles were measured on at least three locations along the case, and the average value was taken. F. Tension Test The tensile strength and toughness were measured using a Zwick universal testing machine of 20-ton capacity. The specimens subjected to interrupted boriding were compared with specimens subjected to continuous boriding. Also, specimens subjected to the same heating cycles (as continuous and interrupted boriding) in a protective atmosphere, but without boriding, were also tested for purposes of comparison. The strength and ductility were measured from the stress-strain curves, and the toughness was measured by calculating the area under the curve. G. Wear Tests 1. Pin-on-discadhesive wear test Wear tests were performed using a pin-on-disc machine (Ducom TR20) under unlubricated dry sliding conditions. The disc material was EN24 steel in the hardened condition (65 HRC). The surface roughness of the disc is of fine machined quality. Both the unborided and borided specimens were tested. During the test, the ambient temperature was 303 K. The speed of the disc was 0.6 m/s. The duration of the test was 2.5 hours for each specimen. The Z displacement of the pin under test was monitored using a precision linear variable differential transformer, and the wear losses of the borided and unborided specimens were compared.
METALLURGICAL AND MATERIALS TRANSACTIONS A

2. Faville Levally test The Faville Levally (Falex) test machine, shown in Figure 4, is a special wear-testing machine used for the evaluation of the scuffing or scoring resistance of the case-hardened samples. In this test, a specimen of 40 mm in length and 6.5 mm in diameter was attached to the collet by means of a cotter pin, and the collet was attached to the main drive shaft. Two jaws made of EN 45 (AISI 1038) steel, with a hardness of 24(1) HRC and having a 90-deg V-notch, fit into the holes of the loading arm. During the test, these jaws were clamped around the rotating testpiece using the ratchet wheel, and an initial load of 2000 N was applied to the specimen. A load cell attached to one of the loading arms senses the applied load. For each test, a new pair of jaws was used. The main shaft holding the specimen was rotated at a constant speed of 290 rpm by a motor. The load on the specimen was increased continuously through a ratchet wheel attached to a cam fitted to the shaft. The rate of loading was maintained at approximately 100 Ns1. The tangential load was directly measured by means of another load cell. The Falex machine was interfaced with a computer, which continuously monitored the normal load and tangential load during the test. The coefficient-of-friction values were calculated from these data. The test was stopped at the onset of scuffing/scoring, which was indicated by a sharp increase in the frictional value. This is considered the endpoint of the test. In the worst case, the specimen may get welded to the jaws, or the specimen may extrude after reaching the red-hot condition, indicating poor stiffness. When the specimen has the ability to resist scuffing, the specimen gets polished and the V-notches turn into a U-shape, indicating good scuffing resistance.
H. Corrosion Testing A copper chloride accelerated salt-spray corrosion test (also termed the CASS test) was chosen to study the corrosion behavior of the steels. This system should normally employ a salt-spray chamber, but an immersion technique was used as an approximation. 2.6 g of cupric chloride in one liter of glacial acetic acid was mixed thoroughly in a beaker, and the treated and untreated samples were subjected to the corrosion test for a period of 64 hours. After 64 hours, the samples were washed in running water and acetone and then dried. The loss in weight of the treated sample and the untreated sample were measured using a chemical balance, and the corrosion rate in mg/dm2/day was calculated for both the treated and untreated samples.
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Fig. 7X-ray diffraction pattern of continuously borided medium carbon steel.

Fig. 5Optical micrograph of continuously borided medium carbon steel in molten salt (1223 K, 4 h).

Fig. 8X-ray diffraction pattern of interrupted borided medium carbon steel.

Fig. 6Optical micrograph of interrupted borided medium carbon steel in molten salt (1223 K, 4 h).

borided specimen is not due to a lower boron activity in the bath, but it is due to the transformation of FeB to Fe2B, which occurs during the soaking treatment at 873 K (subsequent to boriding). C. Microstructural Modifications on Interrupted Boriding The most conspicuous microstructural modifications on interrupted boriding include (1) nearly spherical interneedle iron-boron-carbon (iron borocarbides) precipitates, (2) carbon segregation at the transition zone (Figure 9), and (3) blunting or a decrease in curvature of the boride needle tip (compare Figures 5 and 6). In interrupted borided specimens, the boride needles are more rounded, thicker, and shorter than in continuously borided specimens. The boride case shows a more uniform case depth in the interrupted borided specimens than in continuously borided specimens. In other words, the variation in the length of boride needles (the difference between the maximum and minimum length) is significantly less in interrupted borided specimens, which is expected to increase the toughness of the case.[24] This observation is found to be common to both pack (both boron carbide and ferroboron processes) and molten salt (borax boric acid) boriding processes. The variation in boride morphology can be explained by strain-energy considerations and carbon segregation at the interface. 1. Strain-energy considerations in influencing boride morphology Very high elastic strains are associated with interstitial boron diffusion, higher than those due to carbon or nitrogen,
METALLURGICAL AND MATERIALS TRANSACTIONS A

III. RESULTS AND DISCUSSIONS A. Microstructural Observations of Borided Specimens A typical micrograph of a continuously borided mediumcarbon steel is shown in Figure 5. The microstructure shows the growth of sharp boride needles of about 150 m in thickness. Figure 6 shows the optical micrograph of interrupted borided medium-carbon steel specimen. This micrograph indicates blunting of boride needle tips and precipitation of nearly spherical interneedle particles. B. The XRD Investigations The XRD investigations of the continuously borided medium-carbon steel (Figure 7) showed the presence of both FeB and Fe2B phases at the borided surface, while XRD investigations (Figure 8) of interrupted borided specimens showed the presence of only Fe2B phase at the borided surface. A boriding treatment after 1 hour results in the formation of FeB phase. Subsequent to boriding for 1 hour, the specimens were held at 873 K for 1 hour. It was observed that deboriding occurred, resulting in the transformation of FeB to Fe2B. Hence, the absence of FeB phase in an interrupted
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Fig. 10Optical micrograph of continuously borided medium carbon steel in pack process (1223 K, 4 h).

Fig. 9Optical micrograph of borided low carbon steel showing carbon segregation in the transition zone.

as the radius of the boron atom (0.097 nm) is much higher than that of carbon (0.077 nm) or nitrogen (0.071 nm). The shape of the second phase (precipitating phase) is generally governed by the balance between (1) the interfacial energy, which is proportional to the interfacial area at the interface between the two phases, and (2) the volume strain energy and chemical free-energy change, which are both proportional to the volume of the new phase created. If the interfacial-energy consideration is the dominant factor, the most preferred shape is the spherical shape, as it is the shape which has the minimum total interfacial energy. This is because the spherical shape has the least surface area per unit volume, the disc shape has the highest area, and the rod or needle shape is in between. Thus, the disc shape would be the least likely, and the rod shape would be more likely to form than the disc shape, based on the interfacial-energy criterion alone. However, if strain energy is the dominating factor, a minimum strain energy would result in a disc or plate shape and a maximum strain energy would result in a spherical shape, and the rod shape would be in between. In the case of the iron borideiron interface, a needle- or rod-shaped growth results, possibly as an optimum compromise, because both the strain-energy factor and the surface-energy factor are active to significant extents. The curvature of the advancing tip of the boride needle may be considered to be determined by strain-energy considerations. In the case of continuous boriding, the strains are likely to be very high, resulting in sharp needles (with very high curvature). On the other hand, in interrupted boriding, strain-accommodating mechanisms operate due to the thermal cycling, and, as a consequence, the tip curvature reduces,
METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 11Optical micrograph of interrupted borided medium carbon steel in pack process (1223 K, 4 h).

resulting in more rounded needle tips and thicker boride needles. 2. Carbon redistribution on interrupted boriding In the transition zone (zone next to the boride layer) in medium-carbon steels, the microstructure shows a difference between the interrupted and continuously borided specimens. The ratio of pearlite to ferrite is higher in the transition zone in interrupted borided specimens, as compared to the continuously borided specimens (Figures 10 and 11). This indicates that carbon segregates more in the transition zone below the boride layer in the interrupted borided specimens than in the continuously borided specimens. It is well known that the solubility of carbon in iron borides is very low, and the diffusion of boron into the matrix can result in significant strains, as mentioned previously. Redistribution of carbon atoms into boron-free regions at the interface of the advancing tip could be a significant strain-accommodating mechanism during boriding. However, carbon redistribution is obviously a kinetically limited phenomenon. During continuous boriding, kinetic factors limit any long-range redistribution of carbon atoms. But, on interrupted boriding, a significant carbon redistribution can take place during the cooling cycles when the temperatures are about 873 to 973 K.
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Fig. 12Scanning electron micrograph of continuously borided medium carbon steel in pack process (1223 K, 4 h).

Fig. 13Scanning electron micrograph of interrupted borided medium carbon steel in pack process (1223 K, 4 h).

The diffusivity of carbon in alpha iron and in austenite are governed by the following relations:[30] Dc 0.2 exp (20,100/RT ) Dc 0.25 exp (34,500/RT ) [1] [2]

The diffusivity values of boron in -iron and in -iron is given by the relations[31] DB 106 exp (62,000/RT ) DB 2 103 exp (21,000/RT ) [3] [4]

al.[32] and Qian and Stone.[19] As the carbon content in the transition zone in interrupted borided specimens is higher than in continuously borided specimens, the advancement of boron perpendicular to the surface into the specimen is slowed down, acicular growth of the boride needles is retarded, and lateral growth is promoted. Therefore, instead of long thin needles, thicker and more rounded needles form. 3. Precipitation of borocarbides Another significant observation on interrupted boriding of medium-carbon steel is the precipitation of new interneedle particles in the interrupted boriding process. The particles seen in the optical micrographs of interrupted borided medium-carbon steel specimens are absent in continuously borided medium-carbon steel specimens. These precipitates are likely to be iron borocarbides, as suggested by Brakman et al.[32] The hardness of these particles is in the range of 1000 HV under a load of 25 g, as is expected for iron borocarbides. Koifman et al.[33] also has reported that shortterm processes produce iron borocarbides and long-term processes produce cementite. According to Brakman et al.[32] when the carbon content ahead of the advancing boride layer exceeds the limit that austenite can dissolve, it combines with boron to form iron borocarbide Fe3(B,C). The presence of interstitials in octahedral sites in fcc austenite results in symmetric distortion, while it results in nonsymmetric tetrahedral distortion in bcc ferrite. This results in restricted solubility of interstitials in bcc, compared to fcc, structures. During boriding, there is a limited solubility of boron in the austenite matrix adjacent to the growing boride needles. During interrupted boriding, when the specimen is cooled to the ferritic temperature range, the significant decrease in solubility can aid the precipitation of borocarbides. The highenergy boride/austenite matrix acts as a potential and effective site for nucleation for the borocarbides. The high fraction of such interfaces results in increased nucleation sites, leading to precipitation of fine and nearly equaixed borocarbides. This explains their presence in interrupted borided specimens in contrast to continuously borided specimens. Usually, it is difficult to distinguish between borocarbides and boride phases by XRD, due to the very small latticeparameter difference. Figures 14 and 15 show the ternary Fe-C-B phase diagram at 1173 and 973 K, respectively. The diagram at low temperature indicates clearly the presence
METALLURGICAL AND MATERIALS TRANSACTIONS A

From Eqs. [1] and [2], it can be computed that the diffusivity of carbon in austenite at 1223 K is 1.71 107 cm2/s and that in ferrite at 873 K is 1.856 106 cm2/s, respectively. In contrast, the diffusivity of boron in austenite at 1223 K is 3.53 107 cm2/s and that in ferrite at 873 K is 3 1010 cm2/s. Carbon diffuses faster in alpha iron than in austenite, whereas boron diffuses nearly 1000 times faster in austenite than in ferrtite. The diffusivity of boron at the austenitizing temperature is approximately twice that of carbon at the same temperature. Hence, selective redistribution of carbon may not be feasible at the austenitizing temperature. However, in the ferritic temperature domain (873 K), the diffusivity of carbon is about four orders of magnitude higher than boron. In general, the lower solubility of interstitials in bcc ferrite results in a higher driving force for interstitial redistribution while holding at 873 K. The relatively higher diffusivity of carbon at this temperature can further aid the relative redistribution of carbon into boron-free regions. This redistribution results in an improved microstructure morphology and lower residual stresses. The precipitation of borocarbides can also be understood as being governed by the influence of temperature on diffusivity, solubility, and precipitation kinetics. Figures 12 and 13 show the scanning electron microscopy micrographs of a continuously borided and an interrupted borided specimen, respectively. The presence of fine cracks in the continuously borided specimen could suggest the presence of high residual stresses in these materials, in comparison to interrupted borided specimens. The high carbon content in the region below the borides (forming as a result of boron diffusion) will invariably slow down the rapid thrust of the advancing boride front, as reported by Brakman et
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Fig. 16Microstructure of the core in continuously borided medium carbon steel in pack process (1223 K, 4 h).

Fig. 14B-C-Fe isothermal section at 1173 K in weight percent.

Fig. 17Microstructure of the core in interrupted borided medium carbon steel in pack process (1223 K, 4 h).

Table I. Grain Size of Steel under Various Conditions


Solution
1
Fig. 15B-C-Fe isothermal section at 973 K in weight percent.

Material
medium carbon steel medium carbon steel

Condition
continuously borided interrupted borided

Grain Size
ASTM 12 ASTM 56

of the phase of the type Fe23(C,B)6, along with Fe3(B,C) at the possible concentrations of boron and carbon in the alloy.[34] The core microstructures are presented in Figures 16 and 17. The grain size of the core is much finer in interrupted borided specimens than in continuously borided specimens. The results are tabulated in Table I. It is further emphasized that the primary objective of interrupted boriding is to redistribute the carbon in a suitable way, so as to reduce the overall strain energy of the system. Such a carbon repartitioning is found to have a direct or indirect effect in modifying the microstructure and morphology of the case, including (1) blunting of boride needle tips, (2) precipitation of interneedle borocarbides, and (3) an enhanced pearlite-to-ferrite ratio in the transition zone.
METALLURGICAL AND MATERIALS TRANSACTIONS A

D. Microhardness The microhardness profiles of continuously borided and interrupted borided specimens are shown in Figures 18 and 19, respectively. The maximum hardness at the surface of continuously borided specimens is higher, compared to interrupted borided specimens. Along the length of the boride needle, there is a greater scatter in hardness; this hardness scatter is much greater in continuously borided specimens than in interrupted borided specimens. This difference perhaps indicates a greater inhomogeneity in the boron and carbon concentrations in the continuously borided specimens. This is in good agreement with the earlier discussion, suggesting a constraint on the long-range diffusion of carbon during continuous boriding.
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Fig. 18Microhardness variation within a boride needle (continuously borided medium carbon steel in molten salt process).

In the interrupted boriding process, after every boriding stage, cooling to a lower temperature results in an increased carbon concentration in the transition zone. This zone with a higher carbon content provides additional resistance to further boriding. Karpenko et al.[1] have reported decreased boriding kinetics with an increased matrix carbon content. Due to the increased carbon content in the transition zone, the rapid pincer-like advancement of the boride front is retarded, giving rise to lateral growth of the needles, which also leads to blunting of boride needle tips. Since the sharpness of the needle tips is reduced, the notch effect is also reduced, resulting in improved toughness and ductility of the borided samples. Figures 22 and 23 show the scanning electron micrographs of the continuously borided and interrupted borided specimens subjected to a tension test. The absence of transgranular cracks in interrupted borided specimens indicates their higher toughness in comparison to continuously borided specimens. The continuously borided specimens with greater inhomogeneity in the interstitial concentration and with localized residual stresses, as discussed earlier, would naturally result in the formation of transverse cracks during the tension test.

F. Wear Testing The Falex test results did not show any major difference between the interrupted and continuously borided specimens. However, when the borided samples were compared to the unborided samples of the same composition, there was a great improvement in the scuffing resistance. This is due to the refractory nature of the boride layer, which does not soften at the high (red-hot) temperatures produced as a result of friction generated during wear testing. On the other hand, the untreated sample softens easily due to the high temperatures produced during testing, due to the enormous amount of friction. The surfaces of the untreated and borided samples, along with those of the jaws after the test, are shown in Figure 24. The figure clearly shows the contrast between the rough surface of the untreated sample and the smooth surface of the borided sample after the test. More importantly, in all the samples, the boride layer was found to be intact even after the Falex test. A typical micrograph is shown in Figure 25. Pin-on-disc wear-test data (Figure 26) indicate that continuously borided specimens have better adhesive wear resistance. Perhaps this is because the continuously borided specimens have a higher hardness than interrupted borided specimens.

Fig. 19Microhardness variation within a boride needle (interrupted borided medium carbon steel in molten salt process).

E. Tensile Properties A comparison of tension test results (Table II) also provides very significant and interesting data (Figures 20 and 21). These values show that in almost all cases, the ultimate tensile strength, the toughness, and the ductility are better in the interrupted boriding process, compared to the corresponding continuous process. Although the same trend is seen in low-carbon steel also, the improvement is relatively higher in medium-carbon steel compared to low-carbon steel. The increase in tensile strength, ductility, and toughness of the interrupted borided specimens can be attributed to (1) refinement of matrix grains in the core, (2) blunting of boride needle tips decreasing the notch effect, and/or (3) the formation of nearly spherical borocarbides, signaling the transition from an acicular to spherical boride morphology. Irrespective of the relative contribution of each of these microstructural factors, it is interesting to note that the net effect of interrupted boriding is to result in enhanced ductility and toughness.
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G. Corrosion Testing The corrosion resistances of the untreated, continuously borided, and interrupted borided specimens were compared. The results are presented in Table III. The untreated sample shows a very high corrosion rate compared to the continuously borided sample. The interrupted borided samples show improved corrosion resistance over the continuously borided specimens. This may be due to the reduced amount of residual stresses in the interrupted borided samples when compared to continuously borided specimens.
METALLURGICAL AND MATERIALS TRANSACTIONS A

Table II. Comparison of Tensile Properties under Various Conditions for Medium Carbon Steel
Solution
1 2 3 4 5 6

Condition
continuous heating without boriding interrupted heating without boriding molten salt continuous boriding molten salt interrupted boriding B4C based packcontinuous boriding B4C based packinterrupted boriding

Yield Point (N/mm2)


400 460 500 500 400 500

UTS (N/mm2)
609 729 728 804 677 733

Pct Elongation (N/mm2)


20.6 26.3 10.3 14.5 11.2 14.3

Toughness (N/mm2)
17,280 19,620 16,168 16,920 12,220 16,370

Fig. 20Comparison of stress-strain diagrams (B4C process): (1) continuous heating (without boriding), (2) interrupted heating (without boriding), (3) continuous boriding, and (4) interrupted boriding.

Fig. 22Scanning electron micrograph of continuously borided specimen surface fractured in tension.

Fig. 23Scanning electron micrograph of interrupted borided specimen surface fractured in tension. Fig. 21Comparison of stress-strain diagrams (molten salt process): (1) continuous heating (without boriding), (2) interrupted heating (without boriding), (3) continuous boriding, and (4) interrupted boriding.

the boride layer. The major achievements and conclusions of this investigation include the following. 1. A cost-effective method of boriding using low-cost materials like ferroboron, ferrosilicon, etc., was developed. 2. An interrupted boriding process with improved microstructural morphology and mechanical and corrosion properties was developed. 3. Shorter and thicker boride needles with blunted tips were observed in interrupted borided specimens and long, thin, and sharp needles were observed in continuous boriding.
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IV. CONCLUSIONS Interrupted boriding results in a better microstructure morphology and, possibly, better residual-stress distribution, resulting in a gradual decrease in hardness from the surface toward the core and in improved mechanical properties like toughness and ductility. This new modification to the boriding process is very valuable in reducing the brittleness of
METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 26Pin on disc wear test data at 100 N load. Fig. 24Surfaces of untreated (U) and borided (B) specimens along with jaws after Falex test.

Table III. Corrosion Test Results Material: Medium carbon steel


Solution
1 2 3

Condition
untreated continuously borided interrupted borided

Corrosion Rate (mdd)


200 112 105

seen in the interrupted borided specimens. This also indicates that adopting interrupted boriding in place of continuous boriding can reduce brittleness. Also, the tensiontest results indicate higher toughness and ductility in the interrupted borided specimens. 7. A higher corrosion resistance was observed in interrupted borided specimens than in continuously borided specimens.
Fig. 25Borided layer intact in the specimen after Falex test.

ACKNOWLEDGMENTS The authors express their gratitude to Drs. Baldev Raj and V.S. Raghunathan, Indira Gandhi Centre for Atomic Research (Kalpakkam), and Dr. N. Krishnaraj of M/s Tribology India Ltd. for extending their testing facilities for this research work. They sincerely thank Dr. P. Radhakrishnan, Principal, and the management of PSG College of Technology for extending the facilities to perform this research. The authors thank Dr. P.C. Angelo, Professor and Head, Metals Testing and Research Centre, PSG College of Technology, for his encouragement and invaluable support. This work was partially supported by a project from the Department of Science and Technology and our thanks are due to Mr. V. Raghupathi and Dr. Agarwal, DST, for their encouragement and support. REFERENCES
1. G.V. Karpenko, V.I. Pokhmurovskii, V.B. Dalisov, and V.S. Zamikhovskii: Influence of Diffusion Coatings on the Strength of Steel.
METALLURGICAL AND MATERIALS TRANSACTIONS A

Also, small rounded borocarbides were seen in the transition zone of the interrupted borided specimens. These precipitates were not observed in the transition zone of the continuously borided specimens. 4. In the interrupted borided specimens, at the transition zone, the pearlite-to-ferrite ratio is higher, suggesting higher carbon segregation in comparison to continuously borided specimens. 5. The microhardness values in the boride needles are more uniform in interrupted borided specimens, whereas more fluctuation and variation is observed in continuously borided specimens. This suggests a more homogeneous redistribution of interstitial boron atoms in interrupted boriding. 6. A large number of transverse cracks were seen in the boride needles of continuously borided specimens after tension testing, while significantly fewer cracks were
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2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17.

Trans Tech Publications, Aedermannsdorf, Switzerland, 1979, pp. 19-37. J. Subramanyam: Met. News. 1986, vol. 8, pp. 3-7. C.H. Faulkner: Advanced Materials and Processes, vol. 4, 1999, p. H 43. N.G. Kaidash and V.I. Pokhmurskii: Sov. Mater. Sci., 1965, vol. 1, pp. 487-89. V.I. Pokhmurskii, R.G. Vagula, Y.S. Gribovskii, and V.S. Zamikhovskii: Protective Coatings on Metals, Plenum Publishing Corp., New York, NY, 1973, vol. 5, pp. 236-39. C. Badini, C. Gianoglio, and G. Pradelli: Metall. Italiana, 1987, vol. 79 (10), pp. 747-56. D.N. Tispas and J. Rus: J. Mater. Sci. Lett., 1987, vol. 6, pp. 118-20. M.R.S. John and A.F. Sammels: J. Mater. Sci. Lett., 1981, vol. 16, pp. 2327-29. Y.A. Alimov: Protective Coatings on Metals, Oxonian Press Pvt. Ltd. New Delhi, 1986, vol. 8, pp. 83-85. D.N. Tsipas, J. Rus, and H. Noguerra: Conf. Proc., Heat Treatment 87. The Institute of Metals. London, May 1115, 1988, pp. 203-10. A.G. Von Matuschka: Boronizing, Heyden and Son Inc., Philadelphia, PA, 1980, p. 23. A.P. Epik: Boron and Refractory Borides, Matkovich, Springer-Verlag, Berlin, 1977, pp. 597-611. G.I. Belyaeva, S.N. Stotskaya, N.G. Ilyushchenko, A.I. Anfinogenov, and I.G. Kagan: Protective Coatings on Metals, Oxonian Press Pvt. Ltd. New Delhi, 1986, vol. 8, pp. 61-66. H.C. Fiedler and Richard J. Sieraski: Met. Progr., 1971, Feb., pp. 101-07. A.V. Byakhova, V.F. Loskutov, V.G. Permyakov, A.M. Pogosyan, and I.K. Trush: Prot. Coatings Met., 1986, vol. 12, pp. 72-75. Seong Ho Han and John S. Chun: J. Mater. Sci., vol. 15, 1980, p. 1379. A. Ozsoy and Y.M. Yaman: Scripta Metall. Mater., 1993, vol. 29, pp. 231-36.

18. K. Matiasovsky, M. Cherenkova-Paucirova, P. Fellner, and M. Makyta: Surface Coating Technol., 1988, No. 35, pp. 133-49. 19. L.L. Qian and G.A. Stone: J. Mater. Eng. Performance, 1995, vol. 4 (1), pp. 59-62. 20. T.S. Eyre: Wear, 1975, vol. 34, pp. 383-87. 21. D.N. Tsipas and C.P. Perez: J. Mater. Sci. Lett., 1982, No. 1, pp. 298-99. 22. P. Goeuriot, F. Thevenot, and J.H. Driver: Thin Solid Films, 1981, vol. 78, pp. 67-76. 23. L.S. Lyakhovich: Protective Coating on Metals, Amerind Publishing Co. Pvt. Ltd. New Delhi, 1984, vol. 6, pp. 83-90. 24. G. Palombarini and M. Carbucicchio: J. Mater. Sci. Lett., 1984, vol. 3, pp. 792-94. 25. L.S. Lyakhovich and S.S. Bragilevskaya: Protective Coating on Metals, Plenum Publishing Corp., New York, NY, 1970, vol. 2, pp. 123-27. 26. N.G. Kaidash, P.P. Chastokolenko, V.S. Tatarchuk, L.A. Semeneko, A.A. Parlyukor, and G.A. Bovkun: Prot. Coating Met., Plenum Publishing Corp., New York, NY, 1972, vol. 4, pp. 149-55. 27. C.H. Xu, J.K. Xi, and W. Gao: Scripta Mater., 1996, vol. 34 (3), pp. 455-61. 28. P.A. Molian and H.S. Rajasekhra: Surf. Eng., 1986, vol. 2 (4), p. 269. 29. P. Gopalakrishnan, P. Shankar, R.V. Subba Rao, M. Sundar, and S.S. Ramakrishnan: Scripta Mater., 2001, vol. 44, pp. 701-12. 30. G.F. Carter: Principles of Physical and Chemical Metallurgy. ASM, Metals Park, OH, 1979, p. 243. 31. Paul E. Busby and Cyril Wells: Trans. AIME. J. Met., 1954, vol. 200, p. 972. 32. C.M. Brakman, A.W.J. Gommers, and E.J. Mittemeijer: J. Mater. Res., vol. 4 1989, p. 1364. 33. I.S. Koifman, T.V. Egorshina, and G.V. Laskova: Metall. Term. Obr. Metall., 1969, No. 2, pp. 59-60. 34. V. Raghavan: Monograph Series on Alloy Phase Diagrams. Indian Institute of Metals. 1992, pp. 287-96.

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