Boron effects on the solidification of steel during continuous casting The addition of boron to steel introduces the possibility of steel lly completely solidifying and then remelting in the Interdendritic regions at very low carbon levels. For all carbon levels, a low melting Fe alloy exists as a liquid down to around 1100'C. This a1 low as 0,0004% boron due to the boron is found in steel with segrogation. The persistence of this liquid leads to hot shortness, breakouts, and othor casting defects. Pseudo-binary phase ns have diagrams for low boron concentrat been developed using ThermoCale software ond were confirmed using experimental techniques. L} = EXTENDED ABSTRACT Iris general knowledge that the addition of boron to steels can cause dificuties when irying to cast steel continuously. Unfortunctely, 0 literature search did not uncover any phase diagrams atthe extremely low boron contents found in commercial steels that might explain the cause of these casting defects. Therefore the phase diagram for the FeB system and pseudo-binary phase diagrams for the same system with various carbon contents from 0 to 1 weight percent were constructed using @ commercial computer thermodynamics program, ThermoCale, for this range of boron content. The calculated equilibrium binary phase diagram features the prediction of a metatectic reaction. This reaction oceurs at boron levels of 0.022% and above. Between 0.022% and 0.045% B, solid 6 + y transforms into o mixture of iron rich liquid plus ¥ upon cooling. Above 0.045% boron, the liquid + 8 region transforms into a (liquid + y] region hence remelting is encountered below about 1360 °C. In this range about 1% of the steel will partially remelt and become liquid again. The amount of liquid inthe (liquid + y) region increases afte the transformation as the temperature decreases. This liquid will have boron content about 1.5% cond it will most likely appear at groin boundaries and prior interdendritic regions where B will be higher due to segregation. This newly formed liquid will remain until the temperature is about 1175 °C. This means thot liquid will be present near or atthe surface of the cast product through the upper sections of mos! continuous costers until the stand is around the straightener. The region from 0.022 to 0.045% B will be expanded slightly becouse steel with ‘about 0.013% B will form & iron with over 0.022% 8 after centering into the Y + 8 region from the single phase 5 region. There will also be postmetotectic remelting that will cccur below 1360 °C when solid ¥ transforms into liquid + Y. This will occur from about 0.015% B to 0.022% B Peeudotbinary phase diagrams for carbon levels of 0.05 to 1.0% show that as the amount of carbon increases, the curvature of the Y region decreases, the onset of remeliing decreases, ond the range over which remelting occurs decreases while the final liquid disoppears et about the same temperature. The metotectic region disappears ‘aly ened foro presentation othe 2008 ATS Intemational Seeimoking Conference that hos been concled lo Bovor de Métalgia CIT - Ddcembre 2008 409CONTINUOUS CASTING Effets du bore sur la solidification PM elet rar madt lteter tft) Uajout de bore dons lacier fait apporaitre lo possibilié dobtenir une réaction métalectique, c'esto-dire un acier initolement complétement solidifié qui refond ensuite ux joints de grains et dans les zones interdendriiques, pour des feneurs en carbone tras basses, <0,005% et des niveaux de bore >0,015%. Cotte refusion se produit pour de trés basses teneurs en carbone lorsque le solide Y + 8 se tronsforme en Y + liquide aux environs de 1350 °C. Pour ces trés bosses feneurs en carbone et pour toutes les feneurs en carbone plus élevées, il exsto un composé Fe 4 bos point de fusion qui reste liquide jusqu'aux clentours de 1100 °C. On trouve ce liquide dons les aciers cv bore pour des teneurs en bore aussi basses que 0,0004% pour les toneurs en carbone plus élevées bien que le diagramme de phases pseudorinaire & Iéquilibre nindique pas que la phase liquide devrait sre Cela est do & lo s6grégation du bore aux jojns de grains et dans les zones interdendriiques et & la lenteur de so cedisiribution & partir do cos zones. La persistance de la phose liquide jusqu’s 19100 *C ov moins pendant la solidification provoque between 0.05 ond 0.1% C. The post metatectic remelting disappears at about 1.0% C due to the negative curvature of the y region disappearing at this point. For all corbon levels, if the boron content is above about 0.015% liquid wall remain until a temperature between 1120 to 1170 °C under equilibrium conditions. Therefore casting ony carbon level with over approximate 0.015% boron should lead to possible external and internal casting defects. This boron level is the critical level for a ternary alloy of FeB.C. is level will decrease when segregation occurs during solidification and the extent fo which it is decreased will depend upon the solidification conditions. Also, the phase regions of interest will be altered as further elements are ‘added as would be the case for most steel alloys. The accuracy of the ThemoCale predictions was verified by moking a series of statically cast experimental ingots with 0.4% Ma ond 0.3% Si at la Revue de Métolurgie CIT. Décombre 2008 une fragilié & choud & ces températures ids basses, une ‘ugmeniation de fa tendonce aux percées et des défouts aussi bien en surface qu’ linlérieur du produit couls Io égolement &é monté que lorsque du bore est ojouté pendant l'élaboration de locier, il est trés_ probable guiune partie du bore est oxydé at forme do lecide orique qui pevi reste liquide jusqu's une gomme de empérature de 400 & 600 °C. Ila été mont que la présence dazote jusqu's 150 ppm peu dinfluence sur los caractérstiques de solidification de ees aciers au bore. ‘On discute également delinfluence de aluminium sur les caractérisiques de solidification le logiciel de calcul thermedynamique ThermoCale @ 16 vilisé pour établir les diagrammes de phases Pseudorincires pour les foibles concentrations on ore correspondant aux aciers coulés en continu, Ces diagranmes de phases ont ensuite été valdés ou moyen de plusieurs techniques expérimentoles. Les effels dv bore tur Ja structure brute de coulée de produits industriels coulés en continy ont été confirmés. carbon levels of 0, 0.3, and 0.8% carbon with boron levels ranging from 0 to 0.05%. Material from each Ingot was run on the Differential Scanning Calorimeter (DSC) and Confocal Scanning Loser Microscope (CSLM) for verification. The CSLM analyses showed thot a low melting iron-boron alloy was present in all carbon levels down to a boron concentration of 0.0005% which is much lower than expected from the equilibrium phase diagrams. Examination of commercially cast materials showed boron enrichment as high os 16 times the bulk composition near grain boundaries and inter-dendritic regions which explains the existence of the low melting alloy being present at these low levels of boron. Severe internal and external casting defects have been observed in commercially cast steel with as litle as 0.002% boron to date. 610——— Nitrogen additions have been shown to shift the phase diagrams slightly to the right indicating that nitrogen will Ke up some 8 as BN. Aluminum additions at low levels have essentially no effect, but ot high levels Al may stabilize ferrite and thus render 8 more soluble in the solid, This increases the omount of 8 required to form lowmelting liquid and thus decreases the omoun! of liquid at a given B level. Titanivm additions have been shown to be effective in decreasing the detrimental effects of boron additions by combining with boron to form TiB>. = INTRODUCTION {tis general knowledge that the addition of boron to steels can cause difficulties when trying to continuous cast steel, The difficulty can manifest itself as surface depressions, ridges, pockets, and bleeds. Boron con alse cause internal voids, internal cracks and center looseness No detailed binary phase diagrams for the iron boron system for boron contents found in steel are available in the literature. Therefore there is no information available to assess the cause of the boron induced costing defects Unfortunately, the only phase diagrams found for this system did not look in detail at the boron contents of interest to steelmakers, 0 to 0.01 weight percent boron (1,2), Kubaschewski (2) does provide partial information regarding the Fe-B binary system Figue | shows a reproduced close-up of Kubaschewski’s diagram in the solidification region. The number 0.5 ot the lower end of the deltaserste region represents the boron content in atomic percent and corresponds o about 0.1 w/e boron. Kubaschewski's diagram also shows {hat the temperature of the three-phase region, 138) °C, is below, not between, the limits of the deliferrite range for pure iron. This indicates that the Fe-B system undergoes a melatectic reaction whereby additional 8 stomic percent Fa: 1+ Pert ofthe Fe binary equilsium phose diagram as given by Kubaschewaki a. to Revs de Métalurgia- CIT Décombre 2008 liquid forms (instead of liquid being consumed) os the deltoferrite transforms to ustenite. This will be seen fo have major implications for the behavior of boron bearing steels during continuous casting. To completely understand the implications of this unique feature on the solidification of steel with boron, the phase diagram for the FeB system was constructed for the range sf boron content found in steel and then the pseude-binary phase diagrams for the same system with various carbox contents from 0 to 1 weight percent constructed to fil the void of information for this important element for steel product design This work was thon expanded by looking of the pseudo. binary phase diagrams for three different carbon levels (0%, 0.3% and 0.8% C} with some manganese and silicon additions similar to those found in steel. Alter estoblishing the phase diagrams, ingots were cost with these some carbon contents and boron contents from 0 to 0.05%, and experiments were conducted on these ingots to verity the phase diagrams and to document the effects of boron additions on the properiies of these ingots. Samples from commercial continuous cast boron steels were then investigated to see if similar effects were noted on commercial continuous cast steels. The results of this work are reported below. = EXPERIMENTAL TECHNIQUE The thermodynamic software "ThermoCale, Windows version 3° (ThermoCale} was used to construct all phase diagrams. The software is setup to calculate pseudo binary phose diagrams by specifying which element should be the independent varioble ond entering the weight percent of each individual element in the alloy except for boron. Pseudo-binary phase diagrams for the ironboron system were developed for 0, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8 and 1.0% carbon contents with onboron varying from 0 to 0.1%. Three additional pseudo binary phase diagrams for the ironboron system were developed using for 0, 0.3 and 0.8% carbon contents with 0.4% Mn and 0.27% Si and the boron contents varying over the some range as before 0 to 0.1%. A series of statically cost experimental ingots were produced to investigate the effects of boron additions above 0.004% on steels with o nominal manganese composition of 0.4% and silicon content of 0.3% ot carbon levels of 0, 0.3, and 0.8% carbon, Ingots weighing 45 kg were cast using a vacuum induction furnace. The ingols were photographed after being cast without any conditioning to record the surface appearance of each casting. The ingots were then cul longitudinally into four equal sections and sandblasted to clean the cast surface. The four sections ofthe casting were reassembled into their original configuration and photographed again to record the surface appearance One of the four pieces from the centerline of each ingot was then surface ground in preparation for deep etching in hot HCI to bring out the cost structure. The etched sections were photographed to record the cost structure. After the cast structure was recorded, a small section of the etched piece wos removed near the casting surface ‘and mounted to be examined metallographically. The ‘cto was examined using an optical microscope with Various lighting conditions and the SEM. Another quarter ‘of each ingot made was used to make up samples for analyses in o differential scanning calorimeter (DSC), Liquid + 8 O CONTINUOUS CASTING high temperature ductility tester and confocal scanning laser microscope {CSLM). One somple from each ingot was run on the DSC to determine the location of the phase changes occurring for that particular olloy. A second sample was run in a CSLM at Carnegie Mellon University to observe the behavior of the alloy on heating to liquid and upon subsequent cooling, A 1523 grade slob cast on an ArcelorMittal USA commercial CSP thin slab caster wos sectioned and deep ciched to see the effect of boron on the cast structure for this type of caster. High temperature ductility specimens were produced from the same material and used to determine the reduction in area as a function of deformation temperature witha sirain rate of0.005 cm/sec ‘and reheat temperatures of 1200, 1250 ond 1300 °C. = RESULTS AND DISCUSSION The phase diagram for the binary system Fe-B derived from ThermoCale is shown in figure 2, Although some of the boundaries are different from Kubaschewski’s, most notably maximum boron level in the 8 phose, the calculated ond literature diagrams agree in oll mojor respects including the prediction of o metatectic, reaction. The reaction that causes casting problems in the Fe-C system (3) is when liquid + 3 goes to y+ 5. The buckling of the solidifying shell is caused by the liquid solidifying simultaneously os two different solids with different linear coefficients of expansion. In the ai Liquid +7 (Matatects Reaction [Post metalecic remeling as 8 Solubiiy in y decreases ig. 2- The Fe binery equilibrium phase diagram as predicted by ThermoCale. le Bone de Métlbrgis CIT - Déconbre 2008 onLigue 1 system the y + 5 region forms from only 8 iron, Lew, this system has its own unique characteristics vluch will lead to problems when casting. the most sshvious characteristic is the presence of @ region on the phirse diagram from about 0.022 to about 0.045% W\ whew steel which is Fully solid and o mixture of the y+} phases tronsforms to liquid + Y and hence ‘unynlting is encountered below about 1360 °C. lu this ronge about 1% of the steel will partially twinell and become liquid again. This is the metatectic ‘wortion. This liquid will have boron content about | 4%. and it will most likely appesr al grain boundaries «ad prior interdendritic regions where B will be higher thw to segregation. Is newly formed liquid will remain until the twinparature is about 1175 °C, closely matching the 1177 °C reported by Kuboschewski (2). This means that liuidl will be present near or at the surface of the cast ywauluct through the upper sections of most continuous ‘ustors until the strand is round the straightener, The royion from 0,022 to 0.045% B will be exponded slijhtly because steel with about 0.013% B will form {5 inon with over 0.022% B after entering into the Y + B region from the single phase 8 region. There will hilo be postmetatectic remelting that will occur below 1560 °C when solid ¥ transforms into liquid + y. This will occur from about 0.015% B to 0.022% B. joudo-binary phase diagrams for the Fe-B system with various carbon contents Iho pseude-binary phose diagram for the Fe-B system Is shown for 0.05 weight percent corbon in figure 3. Jn this carbon content the region in which the 100% sulid Y + 8 region transforms into liquid plus solid gion begins at o slightly lower B content and is svor-a smaller B range. In this case, it runs from Iu towe de Metallic CIT Décermbre 2008 is 5 fio Reon] cobout 0.021% B to 0.028% B. The solid region also transforms into a liquid + y + 5 region instead of only @ liquid + Y. It should olso be noted that the lemperoture at which the metotectic remeliing begins is also increased by the addition of carbon, It occurs over the range from 1400 to 1450 °C. The final liquid disappears at about the same temperature as for the 0% C phase diagram (fig. 2). Post metatectic remelting when solid Y transforms into liquid + Y will occur over the same range as for 0% carbon, 0.015 to 0.022% 8B. However at this carbon composition, the curvature of the Y region that borders the liquid + Y region begins to contain @ knee in curve above which liquid + Y exist. Al or near the knee solid Y will exist and below this knee the material will again remelt and transform into liquid + Y again, This knee is ot about 1340 °C for this carbon level. Somewhere between @ carbon level of 0.05 ond 0.1% C the metatectic reaction will no longer occur. Figure 4, the pseudo-binary equilibrium phase diagram for 0.1% C, illustrates this point. However, the curvoture of the Y region that borders the liquid + region now has @ distinct knee in it which means that steel will form liquid + y then solidify os y iron and then cemelt to form liquid * Y again. This occurs at a sufficiently low temperature when the solid y boundary is sloping downwards to the left. This is the same type of remelting thot was seen below the metatectic point in the Fe-B binary phase diagram This remelting begins ot the knee of the boundary curve, and oceurs from about 0.014 to 0.02% B. The remelting will begin much lower thon observed for 0.05% C. It will start at about 1300 °C. o19CONTINUOUS CASTING predicted by ThermoCale. ques 5 predicted by ThermoCale. ‘As the omount of carbon increases in the Fe-C-B system, the curvature of the Y region decreases, the onset of remelting decreases, and the range of remelting decreases while the final liquid disappears «at about the same tempercture, For the pseudo-binary equilibrium phase diagram for 1.0% carbon fig, 5) there is virtually no knee fon the curvature of the Y region and hence no remelting thot occurs. The final temperature ot which liquid disappeors is ebout 1120 °C. the psevdo-binory phase diagrams for 0.2, 0.4, 0.6, and 0.8% carbon can be found in reference (4. lo Revue de Metolungie-CIT- Oécembre 2008 equilibrium phase diagram fer Fe-B with 0.1% ¢ 5- Pseudotinary equilibrium phase diagram for Fe-B with 1.0% C For all carbon levels, if the boron content is above about 0.015% liquid should remain until @ temperature of between 1120 to 1170 °C under equilibrium conditions. Therefore casting any carbon level with over approximate 0.015% boron should lead to possible external and internal costing defects. This boron level is the critical level for a ternary alloy of Fe-BC. This level will decrease when segregation occurs during solidificotion ond the extent to which it is decreased will depend upon the solidification conditions. Also, the phase regions of interest will be oltered as further elements ore added as would be the case for most steel alloysNy. 6 0.27% Si. predicted by ThermoCak. 0.90 €-0.40 Min-0.27-Si-0.0x B nd 0.27% Si as predicted by ThermoCele. Maeudo-binary phase diagrams for the Fe-B-C m with various alloy additions |v invostigote the effects of additional olloys on the tniypation of the phase region of interest, a steel containing (ds Mn and 0.27% Si was investigated with 0.0, O:1, and 0.8% corbon. Figure 6 is the pseudo-binory lu 0% carbon. This can be compared to figure 2 tu observe the effects of the Mn and Si additions, The Y 1.8 solid region that transforms into Y + liquid runs Innm about 0.022 to about 0.045% B for figure 2. This royjion runs from about 0.02% to 0.045% when Mn tl Si ore added fo the system. Remelting begins below silout 1360 °C in figure 2 ond is approximately the sume for figure 6. In this range about 1% of the steel will remelt and become liquid ogain. The newly formed liquid will remain unil the temperature is obout 1175 °C fox both figures. For figure 2 the region from 0.022 to 0.045% B will be expanded slightly becouse steel with owe da Métolurgi- CIT-Décembre 2008 Liquid + v joude-binary equilibrium phase diagram for FeB with 0% €, 0.4% Mn and ‘equilibrium phase diagram for Fe-B with 0.3% C, 0.4% Mn about 0.013% 8 will form & iron with over 0.022% 8 after entering into the Y + © region from the single phase 8 region. For figure 6, steel with about 0.010% B will form 3 iron with over 0.02% 8 after entering inlo the Y + region from the single phase 8 region. Postmetateciic remelting occurs below 1360 °C and from about 0.015% B to 0.022% B in figure 2. Similarly, postmetotectic remelting occurs below 1360 °C and from about 0.015% B to 0.020% B in figure 6. Therefore the effective region for remelting will have to be determined for each steel composition of interest due to change in the phase diagrams induced by alloy additions to the simple ternary, Fe-C-8, system. The dashed vertical lines in this and the next two figures indicate the boron contents of the olloys produced in the vacuum furnace. Figure 7 is the pseudo-binary for 0.3% carbon and the same alloy additions as for figure 6. For the addition os0.80 C-0.40 Mn-0.27-Si-0.0x B " CONTINUOUS CASTING Taga Liquid + y ‘ond 0.27% Si as predicted by ThermoCale. of 0.3% the some effects can be seen as in the series of FeB-C diagrams. The metatectic reaction is not seen at this carbon level ond the knee in the Y region appears causing remelting below IKis point. Remeliing as o result of the knee in the y phose region occurs from about 0.01 to 0.015% B and the remelting will begin at about 1300 °C. The final liquid disappears ot about 1140 °C. Figure 8 is the pseudo-binory for 0.8% carbon and the same alloy additions as for figure 6. This can bbe compared to the pseude-binary equilibrium phase diagram from reference (4) to observe the effects of the Mn and Si additions, For the pseude-binary phase diagram without the manganese and silicon additions remelting os 0 result of the knee in the Y phose region occurs from about 0.012 to 0.014% B and the remelting will begin ot about 1225 °C. The final liquid disoppears ct about 1140 °C. For figure 8 remelting os 0 result of the knee in the Y phose region occurs from about 0.007 to 0.009% 8 and the remelting will begin at about 1200 °C. The final liquid disappears ot about 1075 °C. This again confirms that the effective region for remelting will have to be determined for each steel composition of interes. Surface appearance of cast ingots The shotblasted surfaces of the as-cast ingots showed ‘on increase in surface defects as the amount of the Le Revue de Matalin CIT - Ddcembe 2008 boron additions increased irrespective of the carbon content, An example of this deterioration is shown in figure 9 thot compares © 0.3% C ingot with no boron to an ingot with 0% C and about 0.05% boron. In general it oppecrs that the surface quality degrades as the amount of boron in the alloy increases due to the increased incidence of folds, pockets, and ridges indicative of liquid seepage after the formation of the original cost surface. This general observation of boron degrading the surface quality of a casting fits with the observations of the as-cast surface quality (0:2863% 0, 0% B Fig. 9- As shot blasted surface of ingots with ne boron cond 0.05% boron. 66«al continuously cost slabs produced on commercial Mhotomicrographs of the ingot structure near the cost swiface, stchod with ital using an optical microscope Ih 10) shows the cast structure of the 0% carbon steel twit the cast surface etched in 2% nitol of 9x using the syst mictoscope for both 0% boron and the highest (evel sl boron for this corbon level (0.05%) under the uimin lighting condiions. There is @ white phase near thw grain boundaries for the 0.05% boron alloy which imu be @ boron rich ironboron alloy. The amount ofthis ius Increases with increasing boron content. The grain Inuries of the highest carbon level investigated, 0.8%, wnie examined at high magnification, 1000x, and does not ‘how the presence of any carbide in the grain boundaries ‘even at this high carbon level indicating thot the white Inlune ot the grain boundaries is not a carbide (fig. 11). DSC analyses of alloys ‘A sumple from each alloy was placed in the DSC unl heated from room temperature to 1600 °C and ‘nuled down to 500 °C, reheated to 1600 °C and than cooled down to room temperature at a heating snd cooling rate of 10 °C/ min, The cesults for all 0% ‘aibon alloys are summarized in fgure 12. The peaks hnoted upon heating and cooling are super imposed on lop of the pseudo-binary phase diagram derived from IhermeCele. The peaks on heating closely define the phase boundaries between {liquid + 8) and liquid, hwiween (Y + 8) and 3, and between (y + MzB) and (liquid + yl. The pecks om caoling define the phase boundaries between y ond (Y + 8], between (liquid + YI and {Y + 8}, between (liquid + y) and Y, and also hhotween 8 and (liquid + 8) x Paaks on Heating © Peaks on Colin | Fig. 12 DSC results for all alloys containing 0% €. Iw Rowe de Méollgie-CIT-Décombre 2008 0.00 C-0.40 Mn-0.27-Si-0.0x B 0% 6, 0% 8 0% C, 0.05% 8 Fig. 10- 0.05% B, etched in ntl. Fig. 11+ Optical micrograph of 0.8% C, 0.004% B steel Indicating the absence of carbides on the grain structure,The phase boundary between (Y + MzB) ond lliquid + Y} is also defined by the cooling peaks The DSC results show that the ThermoCale prediction is very accurate because the DSC information closely adheres to the ThermoCale predictions. Similar good correlations with ThermoCalc predictions were obtained for 0.3 and 0.8% carbon alloys. Please note thot the DSC tests were performed at 10 °C/min cooling/heating rate, and hence the results obtained were not under equilibrium conditions os were the ThermoCale predictions. Superheating or undercooling will play o role in the disagreement with calculations Confocal scanning laser microscope anclyses of alloys The results of the confocal microscope analysis for the 0% C alloy are shown in figure 13. This is graphical representation of the various phase changes “in-situ” ‘observed during heat and cooling of the sample super imposed on the appropriate ThermoCale pseudo-binary equilibrium phase diagram. The temperature range has been exlended to a lower temperature than used for the ThermoCalc derived phose diagram in order to accommodate additional transformations observed 0.00 C-0.40 Mn-0.27-Si-0.0x B Liquid [xFret Appewares of Ug gs Fig. 19 -CSLM results forall alloys containing 0% C. ‘¢ Alba Gunma Tre. ° : 3 CONTINUOUS CASTING by the confocal microscope. In some instances the additional data can be used to further define the phase diagram beyond thet done by ThermoCale. The results confirm the accuracy of the ThermoCale prediction. For all boron contents at 0% carbon an opaque liquid forms from 1000 to 1390 °C, which is the iron-boron liquid phase. This opaque liquid disappears between 1277 and 1460 °C for all boron contents between 0.0215 and 0.046% os predicted by ThermoCale and the liquid then reappeared loter due to remelting. This did not occur for the 0.0477% boron alloy since it is past the metatectic region. The alloy with 0.0094% boron had the liquid iror-boron alloy appearing at around 1120 °C end disoppearing at between 1405 and 1420 °C. A second liquid phase did not appear at higher temperatures presumably due to the small temperature range over which the predicted remelting would occur ot this boron level The appearance of o liquid at this low temperature was not predicied by the ThermoCale psevdo-binary phase diagram. Therefore its existence can only be attributed to segregation of boron during solidification. Liu +8 “ADiaeppesrere of Ft Liqud w Second Appearance ofgad +.Gaminao Apa Tans.The low melting iron-boron alloy appeared for all boron contents less than 0.0150%, below which the pseudo-binary equilibrium phase diagram predicts that it will not exist. Only the 0% boron alloy did not have ny liquid form before the predicted liquidus Femperature. The lowes! boron level at which the low melting point liquid was observed was 4 ppm and it was olso observed for the 15 and 48 ppm boron levels 08 well as the 94 ppm level mentioned before. This liquid oppeared between 1350 and 1390 °C for the 4 to 48 ppm boron levels and at about 1120 °C for the 94 ppm level It can be concluded for 0% carbon level that the ThermoCale prediction of the phase diagram is accurate cond thot even with very minor boron additions of 4 ppm for more « low melting point iron-boron phase will exis. This iromboron phase will increase the hot shortness of alloys with an increase in boron content, This low melting phase will exist down to oround 1350 °C for boron contents less than 94 ppm and will exist down to about 1120°C for 94 ppm boron and above, It is ‘opparent from the observation of these alloys under the confocal microscope that the volume of the casting occupied by this low melting phase decreases os the boron content decreases and the temperature at which it disappears increases It should be mentioned that the heating and cooling rates during the confocal microscope observation were made manually with core around the ThermoCale predicted temperatures. Therefore, it is believed that the experimental conditions under the CSLM were closer to equilibrium than DSC experiments. Similar good correlations with ThermoCale predictions were obtained for 0.3 and 0.8% corbon alloys. They also confirm the ThermoCole predictions ond have the liquid ironboron eppear al all boron levels except for 0% It should be noted that a tronsporent liquid appeared fon heating in the ronge of 460 to 950 °C ond it disappeared before 1145 °C for the 0 and 0.3% alloys. This transparent liquid is believed to be boric oxide based on the temperature at which it becomes liquid olong with the fact that it is glassy ond eventually disappears. The liquid comes from grain boundaries and interior locations within the grains that appear as inclusions before they become liquid Iwas not noted for the 0.8% carbon alloys or the two commercial alloys. Since only silicon was used for deoxidotion in these lob heats «nd the fact that the free energy of formation of silicon oxido und boron oxide are very similar, it is likely that in these lower carbon alloys boron contributed to the deoxidation of the sieel during steelmoking and hance boric oxide was present in the a Rover ch Mahitnnin 17 RAembve 2008 somples. The fact that the higher carbon steels will have lower dissolved oxygen content is probably the reason it wos not found in the 0.8% carbon steels. Microstructural and Gleeble investigation of commercial CSP continuous cast 15238 steel alloy Figure 14 shows the as-cast surface of a slab section obtained from a thin slab commercial cast of boron containing 15238 steel. This slab section was examined to observe the effect of boron on the slab quality. This cast had only 0.0024% boron but several surface defects con be noted. There are surface depressions on the lower right cond on the narrow face and longitudinal streaks ond depressions over the enlire broad face. Longitudinal macro-samples were made to determine the effect of boron on the cast macro and micro-structure. One of these sections is shown in figure 5 after etching in hot HCl. The structure contains many internal transverse cracks that appear from 12 to 16 mm from the surface. This figure shows that they form belween dendrites where there will be a higher concentration of boron and low melting iron-boron phase and hence © much less dense liquid will form in this region than Fig. 14- Ascast surface ofa slab thin slab caster. 0.0024% Boron ig: 15- Etched longitudinal crossection of the slab shown in Figure 14, casting direction is from left to right. ow16- Etched micrograph of cracks observed in figure 15, in the bulk liquid. This change in density plus the much lower melting point will encourage gravity driven flow nd the formation of channels in the steel due to the difference in liquid densities between the bulk liquid and interdendritic liquid. This phenomenon will occur only when the solidification rate is not very rapid cand this is the reason that the open cracks noted did not form until the casting had exited the mold. For this caster, the thickness of the shell upon exiting the mold is approximately 12 mm Closer inspections of these cracks are shown in figures 16 and 17. These figures indicate that the void surface consists of rounded dendrites of the type that would exist if the liquid present between the dendrites was decanted. This supports the hypothesis that the cracks are channels formed by gravity driven flow. The boron composition for this slab was about 0.0024% and the carbon content was about 0.22%. This indicates thot boron levels as low as 0.0024% will influence the solidification behavior of the steel High temperature hot duciility specimens were made from the same heat and the hot ductility was determined at various deformation temperatures to investigate the effect of boron. The samples were soaked ot three different temperatures (1200, 1250, and 1300 °C) before being cooled and deformed at temperatures of 1100 °C and lower. la Rome de Métolsio CIT Décambre 2008 CONTINUOUS CASTING Fig. 18 - Close-up ph « high-temj froma 15238 The tensile specimens had o reduced cross section ot midlength to encourage the necking of the samples to fracture in this orea ond the thermocouple to monitor temperature was placed in the reduced cross section crea, When soaked at either 1250 or 1900 °C, the samples either broke without a reduction in an crea outside of the reduced cross section or broke within this crea and had a very low reduction in area most of the time. The appearance of this type of fracture is shown in figure 18. 620Fig, 19- Fracture surface from one side of the ightemperature ductility specimen dt oi, One of the fracture surfaces is shown in figures 19. This surface does not show any indication of mechanical deformation while being fractured. The dendrites formed during solidification are easily discerned and they ‘appear slightly rounded on the fracture surface. This indicates the presence of some low melting point liquid during the deformation process. Hints of the presence of this liquid can be seen on both fracture surfaces and this liquid seeped out of the fracture surface during extension and accumulated on the lower surface of one side of the Gleeble specimen and solidified there. This accumulated re-solidified low melting point liquid can be seen in figure 18 near the micron marker on the le Rerue de MétallugieCIT- Décembee 2008 [eons rang Tons SS Tose Haag Tone = TERE Helin Tors Fig. 21 - Hot ductility results for @ 15238 grade cast on @ commercial CSP thin slab caster. lower right side. A close-up of this is shown in figure 20. However, when the soaking temperature wos reduced to 1200 °C this phenomenon did not occur and the specimens broke as expected. The hot ductility results core plotted in figure 21. 15238 The pseudobincry phase diagram for steel determined by ThermoCole con be s figure 22. Since a large quantity of liquid existed when the material was deformed at both 1250 ond 1300 °C but not at 1200 °C, itcan be inferred that the boron content of the segregation interdentrically and at the grain boundaries ‘was between 0,034 and 0.048% based on this phase15238 me CONTINUOUS CASTING Fig. 22- Pseudo-binary equilibrium phase diagram for grade 15238 steel as calculated by ThermoCale. diagram, This means that the boron content in these areas was between 14 to 20 times the bulk content of the alloy This was verified by using an SEM to determine the boron content difference between the bulk and grain boundary areas, This measurement revealed that the boron content in the grain boundaries was 16 times that in the bulk of the material. Therefore the pseudo binary phase diagram determined by ThermoCalc supports the observations and conclusions reached by physically examining the hot ductility specimens. 10 Rew de Méolrge -CIT-Décombre 2008 by Thermos 15258 Luis - vee, Bar | oe ! ‘on V+ M25 + Mas Fig. 23- Proudo-binory equilibrium phase diagram for grade 15258 steel as calculated These observations indicate the phenomena noted in this study done with laboratory prepared alloys exis! in commercial continuous cast boron steels. Figure 23 is the pseudo-binary equilibrium phase diagram for a 1525B grade as o function of boron conteni, the only significant difference in composition for this clloy is an increase in nominal chromium content from 0.04 to 0.15% This slight increase increases the position of the liquidus at the higher levels of boron that would beFe-B-0.00 C-0.010N 1550.0 1500.0 © 1450.9 1400.0 1980.0 1300.0 1250.0 1200.0 1150.0 ‘Temperatur o 0.02 0.04 0.08 Boron Level, w/o ° 02" 0.04 0.06 Boron Level, w/o Fig. 25 Pseudosbinary equilibrium phase di the effect of @ 0.05% expected due to segregation by about 200 °C at 0.1% and about 100 °C at 0.05%. Therefore one method to counteract the detrimental effect of boron is to alter the alloy content by the eddition of elements that will raise the temperature at which the liquidus occurs Investigation of the effect of N, Al, and Ti on the Fe-CB phase diagrams Further theoretical studies were undertaken to determine the effect of nitrogen, aluminum, ond fitonium on the phase diagrams of the Fe-C-B system The effect of nitrogen is shown in figure 24. The original phase diagram for the iron-boron binary is shown by the dashed lines, The alteration due to the nitrogen oddition of 0.01% is shown by the solid lines. thin line indicating the temperature ot which BN will begin to Revue de Métallugie-CIT-Décembre 2008 0.08 oa [—O—Liquidus e— Solidus —O--BN Pptn. | 0.08 on y+M2B [-O-Liidus -@-Sotcs BN Prin yram for « FeB-0.01% N steel indicating ition of Alto the system as calculated by ThermoCale. to precipitate is also shown on this diagram. The addition of this amount of nitrogen shifts the phase diagram to the right by abou! 0.01% boron due to the fact that the otomic weights of boron and nitrogen are almost the same and that nitrogen in this amount will tie up 0.01% of boron as BN. The effect of the oddition of 0.05% aluminum in the presence of 0.01% nitrogen for the same alloy is shown figure 25. The original phase diagram for the iron-boron- 0.01% nitrogen system is shown by the dashed lines. The alteration due to the aluminum addition of 0.05% is shown by the solid lines. The addition of aluminum has essentially no effect because BN siill precipitates preferentially versus AIN at this low Al level.0 SEA ° 0.02 0.04 2.08, Boron Level, wo Fe-B-0.00 C-0.010 N-0.05 ° 0.02 0.04 0.08 Boron Level, w/o The effect of adding o high amount of Al is shown in fgure 26. In this cose it is seen that AIN precipitation does occur at low boron levels, thereby releasing more boron into solution. However, a8 boron level increases in interdendritic zones, 8N precipitation first occurs alongside and then displaces AIN precipitation, The main effect of high Al comes not from precipitation but form the role of Al as a strong ferrite stabilizer Instead of austenite, the low-melting liquid is now in equilibrium with & ferrite where boron is more soluble, It follows that more 8 is required to form the 10 Rew de Métolrgie CIT Décenbve 2008 [-O-Lauidus 8 Soiidus VAIN Ppin. SEN Ppin CONTINUOUS CASTING SEAN Fo. 26; Preudo-inary equilibrium phase dlogram fora ¥eB0.01% N stelindeting the effect of 1.0% addition of Alto the system as calculated ep an 0.08 on y+M2B -O-Lsidus ATW Pp. Sots -O- 182 Poin SPT ost <- BN Ppt | Fie. 27. Praude-inary equilibrium phase diagram for a Fe8-0.01% N steel indicating the fect of «0.08% addition of Tito the system os calculated by Theemotar. low-melting liquid and thus that less low-melting liquid develops ot a given B level The effect of the addition of 0.05% titanium in the Presence of 0.01 % nitrogen for the same alloy is shown in figure 27. The Ti is expected to tie up the N os TIN, thereby releasing the boron. But ThermoCale predicts thot an additional Ti8e precipitate forms and therefore Ti has the net effect of tying up boron. As with high Al, the net effect is to push the remelting reaclion out to about 0.05% B in the interdendritic liquid, but theeee mechanism for the Ti effect (precipitation) is radically different from that observed for high Al (ferrite stabilizotion) = CONCLUSIONS ‘The following conclusions can be reached from this su + Pseudobinary phase diagrams for the FeBC system hove bbeen established for boron levels encountered in steels; «These phase diagrams hve been shown to be accurate by experimental verification; + Boron induces 6 metotectic reaction at low carbon contents; +A low meling irontboron elloy persists down to 1120 to 1170 °C with boron levels as low as 5 ppm; + Additions ofelements other than Fe, C, and B con sigificontly cfect the psoudobinary phase diagrams; “+The presence of the low melting ironboron alloy has been indirectly verified down to between 1200 and 1250 °C in @ commercial cast 15238 steel «+ The effects of boron on the quality of commercial continvous cost steel product were established ‘The amount of boron segregation found in commercial cast produc in the grain boundaries and injerdenditc regions ‘wos determined; «The effects of N, Al, and Ti on the Fe:C-B phase diagrams were determined, N precipitates boron and s0 does Ti when that element is added to “protect” the B, AV at high levels alters the phase structure ond thus makes boron more soluble in the solid phase than would otherwise be the case. Therefore N, Ti, and high levels of Al ll increase the amount ‘of B required to form the low-meling liquid; «+ Methods to minimize the effect of B on cost product quay were established. « ACKNOWLEDGEMENT ‘We would like fo thank the Center for Iron and Steel Research «at Cornegie-Mellon University for allowing us to uilize the Confocal Scanning Laser Microscope. We would alto like to thank Camegie-Melion grodvate students Brion Webler | and George Shannon for their help in conducting the ETE TOTO experiments. REFERENCES IM Honen Conehston of binary alloys 2 eon (prepare to Rovso de Métalurgie CIT - Décambe 2008 nth he cooperation of K Andetko}, MeGrow Hill 1058 [01 ibxchnavonbor poe dagen Spgeea. IN] Singh, (£1 Blare- Hea! ander ond sa ovation no ‘9 mold os [uncon of see carbon confer 04S Aine Open Heath Proceednge 2l S7.p 10.36, Atanne C (KE) Blaze, (0 Lon) (H) Yio The eet of he solace of sla! dung ¢ proceedings of AlSTech 2008, 02s