Applications of Phase Equilibria in Aluminium Alloy Products and Processes P.V. Evans and R.A. Ricks Technology Strategy Consultants
Introduction Aluminium alloys are generally not used in a state of thermodynamic equilibrium many contain metastable precipitates or intermetallic phases with process routes designed to avoid attainment of equilibrium Even alloys relying on solid solution strengthening are usually in a metastable state at their operating temperatures However equilibrium can be of relevance during earlier stages of production, and at high temperature stages Bright field TEM image of metastable β precipitates in AA6061 (Al-Mg-Si alloy) High resolution image down β needle G.A. Edwards et al. Acta Mat. 46, p3893 (1998)
Equilibrium during processing aluminium In some cases the thermodynamic understanding is embedded in the practices in other cases it comes back to haunt us! We will consider a few of examples drawn from the aluminium process stream 1. virtually all aluminium undergoes some form of treatment whilst molten measurement and removal of dissolved hydrogen can be problematic 2. extrusion: a process stream designed around attainment of equilibrium in situ 3. rolled product development: a case of being wise after the event rolling (plate, sheet) smelter metal re-melting melt treatment casting extrusion other semi-fab fabrication secondary metal (recycled) shape casting
1) Hydrogen in aluminium Aluminium melt treatment generally focuses on improving 3 quality attributes dissolved hydrogen, inclusions, alkali metals Hydrogen is the major contaminant controlled by equilibrium considerations Hydrogen is far more soluble in liquid aluminium cf. solid aluminium solidification of a melt containing too much hydrogen results in porosity example of internal porosity visible on machined engine face surface blistering after homogenisation
Effects of porosity Fatigue life is also reduced as porosity increases fatigue life variation with pore size dendrite 47 µm dendrite 22 µm Y.X. Gao et al., Fatigue Fract. Eng. 27, p559 (2004) fatigue failure surface and pore initiation
Porosity in wrought alloys Porosity also causes problems during subsequent fabrication in wrought alloys, e.g. hot mill edge cracking original ingot porosity (AA5182) 50µm 25mm slab hot mill edge cracking reroll (gauge ~10mm) 20 mm
Hydrogen solubility The solubility of hydrogen in pure liquid aluminium is now well established dating back to pioneering work of Ransley, Talbot and others note hydrogen concentration usually expressed as ml. H 2 per 100g aluminium Data shown for solubility in contact with an atmosphere of pure hydrogen log10(s) (ml/100g) D.E.J. Talbot The Effects of Hydrogen in aluminium and its alloys Maney (2004). 1.0 0.5 0.0-0.5-1.0-1.5-2.0-2.5-3.0 T( C) 1000 800 660 500 400 liquid 3320 log 10 S S = 2.22 T 2700 log 10 S L = 2.72 T solid 7 9 11 13 15 10 4 /T (K -1 ) 10 1.0 0.1 0.01 hydrogen (ml/100g)
Expected relationship Equilibrium constant for the reaction between gaseous hydrogen and hydrogen dissolved in molten aluminium H ( ) 2H ( 2 gas Al solution in metal ) equilibrium constant K = eq S p 2 H 2 S p H 2 = activity ~ concentration of hydrogen (ml/100g) = partial pressure hydrogen So we expect the following form for hydrogen solubility: S = K p = eq H S o p 2 H 2 (Sieverts Law) where S is Hydrogen concentration in ml / 100g, partial pressure is in atmospheres S o is the equilibrium solubility in contact with pure hydrogen
What about alloying additions? Some elements influence the solubility of hydrogen in liquid aluminium relatively sparse data available, and even fewer for the effect in solid aluminium Magnesium, titanium and lithium increase hydrogen solubility in liquid aluminium......whilst iron, copper, silicon and zinc reduce the solubility levels Hydrogen solubility (ml/100g) 2.5 2.0 1.5 1.0 0.5 pure aluminium magnesium titanium zinc silicon copper iron So Mg containing alloys pick up hydrogen more readily and harder to degas pure aluminium 0.0 0 5 10 15 20 Element wt.% data from P.N. Anyalebechi, Scripta Met and Mater., 33 (8), p1209 (1995)
Alloy correction factors The simple solubility equation for hydrogen in liquid aluminium needs to be corrected for the alloy composition generally use interaction coefficients for excess solution free energy log( f H Published experimental data extensively reviewed some first order coefficients reliable, second order more variable some concern over Mg data temperature dependence not available for all elements P.N. Anyalabechi, Light Metals, p827 (1998) Alloy hydrogen solubility treated with a correction factor C alloy = 1/f H... ) = k W + k W + k W + k W... f H = hydrogen activity coefficient Mg + k Mg W Mg 2 Mg Cu + k Cu W Cu 2 Cu Si Si Si + k W C.H.P. Lupis, in Liquid Metals Chemistry and Physics, ed. S.Z. Beer (Marcel Dekker, 1972) 2 Si Zn + k Zn W Zn 2 Zn W x = wt.% of x k = 1 st order interaction k = 2 nd order interaction G.K. Sigworth & T.A. Engh, Met Trans B, 13B, p447 (1982) S = alloy C alloy S o p H 2
But where does hydrogen come from? Hydrogen (ml/100g) The solubility of hydrogen is expressed on the basis of equilibrium between the melt in contact with H 2 gas but the partial pressure of hydrogen in the atmosphere is vanishingly small Water vapour provides the source of hydrogen 0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 aluminium can react with water vapour to form alumina and dissolved hydrogen 660 680 700 720 740 760 780 800 increasing water vapour Temperature (C) water vapour pressure (atm.) 0.075 0.050 0.045 0.040 0.035 0.030 0.025 0.020 0.015 0.010 0.005 example conditions 45ºC, 80%RH 35ºC, 90%RH 25ºC, 80%RH 5ºC, 50%RH
It gets worse Molten aluminium will pick up hydrogen from atmospheric humidity But melting furnaces are usually gas-fired 7.5N 2 + CH 4 + 2O2 7.5N2 + CO2 + 2H 2O Combustion products comprise ~15% water vapour H 2 O (allowing for excess air) Hydrogen level (ml/100g) 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 furnace summer winter holding furnace temperatures 650 700 750 800 furnace: combustion water vapour summer: 45 C, 80% humidity winter: 20ºC, 50% humidity Furnace temperature (C)
Typical hydrogen levels exiting a furnace Example shows measured hydrogen levels in melt (ml/100g) exiting furnace, sampled over many hundreds of casts commercial purity aluminium, furnace running at 725-750ºC H (ml/100g) 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 0 100 200 300 400 cast # Generally found that hydrogen levels in melting and holding furnaces are dominated by equilibrium with furnace atmospheres
How much hydrogen can we live with? H 2 (ml/100g) 0.7 0.6 0.5 0.4 melting furnace hydrogen levels holding furnace hydrogen levels The acceptable level of hydrogen varies depends on product and application Furnaces are quite turbulent environments The melt rapidly achieves equilibrium with the local atmosphere 0.3 0.2 0.1 typical commodity wrought products demanding products aerospace products For nearly all applications, the level of dissolved H 2 exiting furnace is too high 0.0 and must be reduced before casting Degassing is the process by which the melt is treated to lower H 2 levels
Hydrogen removal: batch degassing The degassing process bubbles a dry inert gas through the melt the melt tries to reach equilibrium with the gas by mass transfer of hydrogen The kinetics are controlled by local equilibrium at the bubble-melt interface Foseco batch degassing unit H atom in liquid Al H 2 molecule gas bubble Ar atom in gas bubble extent of boundary layer
Mass transfer between the melt and the bubbles Hydrogen is transferred into gas bubbles, recombining as H 2 molecules partial pressure of hydrogen in the bubble stays in local equilibrium with concentration of hydrogen in the boundary layer around the bubble, H i This establishes a difference in hydrogen concentration between the bulk liquid, H b and the boundary layer, H i which then drives mass transfer from the bulk melt to the bubbles hydrogen flux = k A k i = hydrogen mass transfer coefficient (m/s) A i = surface area of bubble i i( Hb Hi ) H b hydrogen concentration in bulk liquid hydrogen partial pressure in bubble (atm.) p H 2 H = i S o P H 2 hydrogen concentration in boundary layer
Batch degassing kinetics The mass transfer and associated local equilibrium boundary conditions, along with re-absorption from the atmosphere, is built into process models 0.45 quantitative understanding of local equilibrium at the bubble-melt interface is crucial 0.40 0.35 model #764 H (ml/100g) 0.30 0.25 0.20 0.15 0.10 0.05 0.00 0 200 400 600 Fluxing Time (seconds) Comparison of kinetic model with trial degassing Al-9% Si Web base degassing model developed for Foseco
Large furnaces the need for in-line degassing Batch degassers work well for small melts (e.g. < 1 tonne) But modern wrought plants cast from 30-130 tonne furnaces casts can take 1-2 hours duration ample time for the melt to up-gas once more in the furnace furnace degassing has become ineffectual and largely abandoned Degassing and up-gassing kinetics in a holding furnace M. B. Taylor, Aluminium 79, (1/2), p44, (2003)
In line degassing Wrought aluminium plants generally use in-line degassers just before casting, allows no time to up-gas before solidification Continuous process where metal flows through a reaction chamber characterised by an average residence time (chamber volume/metal flow rate) In line SNIF degasser www.pyrotek.com
Just how do we measure hydrogen? The levels of hydrogen we are dealing with in solution are rather low 0.1 ml/100g ~ 0.09 ppm or ~ 0.1 gram of hydrogen per tonne of aluminium And yet these levels are measured on line, in real time: all rely on equilibrium A small volume of carrier gas re-circulates through a porous probe in the melt hydrogen diffuses to the gas and recombines as H 2 reaching equilibrium AlSCAN hydrogen measurement Original Telegas system (Alcoa) www.abb.com
Data processing All on-line hydrogen measurement methods entail measuring the partial pressure of hydrogen in equilibrium with the melt we are not measuring hydrogen in the melt directly In order to estimate the concentration of hydrogen dissolved in the melt: 1. temperature used to calculate the equilibrium solubility for H 2 in pure Al 2. measured p H 2 used to calculate the H level in the melt (assuming pure Al) 3. calculated concentration corrected for effect of alloying elements on H solubility 0.6 H ml/100g 0.5 0.4 0.3 0.2 0.1 0.0 Al Al-5Mg Al-10Si 0 0.05 0.1 0.15 0.2 0.05 atm. H 2 pressure converts to three different H levels, depending on the melt composition so measurement devices rely entirely on knowledge of equilibrium H solubility, and its variation with alloy pp HH2 2 (atmospheres)
Current issues: aluminium and hydrogen Uncertainty over interaction parameters affects our ability to both measure gas levels on line reliably, and control degassing processes the effect of magnesium is probably the most worrying There are a reasonable amount of data concerning hydrogen solubility in pure liquid aluminium, and some data for a selection of binary alloys but hardly any for fully commercial alloys Binary interaction coefficient contributions are assumed additive very limited evidence suggests this may not always be the case: P.N. Anyalebechi, Scripta Met and Mater., 33 (8), p1209 (1995) Hydrogen solubility (ml/100g) 2.50 2.00 1.50 1.00 0.50 7050 exp 7050 predicted 0.00 700 750 800 850 900 Temperature (C) Hydrogen solubility (ml/100g) 2.00 1.80 1.60 1.40 1.20 1.00 0.80 0.60 0.40 0.20 0.00 700 750 800 850 900 Temperature (C) Al-4Cu-0.9Mg-0.5Si exp Al-4Cu-0.9Mg-0.5Si predicted
To help protect your privacy, PowerPoint has blocked automatic download of this picture. 2) Extrusion processing
Extrusion alloys (6xxx) Most common extrusion alloys are based on the Al-Mg-Si system (AA6xxx) often with additions of Cu, Mn Precipitation hardening system, based on the Al-Mg 2 Si pseudo-binary 1.4 1.2 1 AA6061 balanced alloys AA6082 wt% Mg 0.8 0.6 AA6063 0.4 0.2 0 AA6060 AA6005 350MPa 300MPa 150MPa 200MPa 250MPa 0 0.2 0.4 0.6 0.8 1 1.2 1.4 wt% Si
Al-Mg-Si phase diagrams The area of interest is the aluminium rich corner of the Al-Mg-Si system Aluminium solid solution isotherms Pseudo-binary section 2.0 1.8 1.6 1.2 1.4 balanced alloys 1.0 0.8 Al 0.6 0.4 0.2 550ºC 500ºC 400ºC 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 wt.% silicon J. Zhang et al, Mat. Sci. Tech. 17, p494 (2001)
Extrusion process route: homogenisation melting melt treatment casting homogenise & cool preheating extrusion quench age Extrusion logs are homogenised after casting, typically >570ºC dissolution of soluble Mg 2 Si eutectic (quick) formation of Mn dispersoids, and phase transformation of cast intermetallics (slow) 700 Temperature ( C) 600 500 400 300 200 Al solid solution AA6060 AA6063 AA6061 H. Feufel et al, J. Alloys & Comp. 247, p31 (1997) 100 0 wt% Mg 2 Si 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
Cooling after homogenisation Note: no formal solution heat treatment stage in the process route It might be thought quenching rapidly after homogenisation would be desirable preserving Mg and Si in solid solution retaining it during extrusion and quenching, maximising the ageing response Perhaps surprisingly, a slower cooling rate is usually deliberately applied resulting in extensive fine re-precipitation of β -Mg 2 Si needles (note these would be very over-aged in terms of final mechanical properties) Quenched after homogenisation: Mg and Si retained in solid solution R.A. Ricks et al, Extrusion Technology 1992, pages 57-69 1µm Controlled cool after homogenisation (350 C/hr): nucleation of β -Mg 2 Si needles
Preheating and extrusion So what is the point of encouraging precipitation prior to extrusion? The extruders have come up with a cunning plan: Having the solute out of solution before extrusion lowers the flow stress so they can extrude faster on a given extrusion press But a correct selection of billet preheat temperature, combined with the heat of deformation, will carry the extrudate above the solvus re-dissolving the precipitates, just before the extrudate is quenched container deformation heating occurs here quench ram billet die
Effect of cooling rate from homogenisation on flow stress water quench controlled cooling S. Zajac et al., Mat. Sci. For. 396-402, p399 (2002)
In situ re-solutionising This process allows maximum press productivity whilst still ensuring maximum strengthening potential during subsequent ageing Hence precipitates formed after homogenisation must not be too coarse otherwise they won t re-dissolve in short time available above the solvus temperature rise due to deformation takes billet above solvus temperature for the alloy Temperature ( C) 630 600 500 400 300 200 100 0 0 5 10 15 20 25 30 melting starts (solidus) Mg and Si in solid solution (solvus) preheat induction furnace 100 C/min extrusion Time (mins) quench critical quench range
Potential problems (1) The amount of deformation heating depends on the details of the extrusion mainly the extrusion ratio (strain) and the strain rate (extrusion speed) So operating practices need to be fine tuned for each product to ensure the extrudate achieves a temperature above the solvus but below the solidus: otherwise incipient melting is observed and more concentrated alloys have a diminishing operating window: Temperature ( C) 700 600 500 400 300 200 Al solid solution 50ºC AA6060 150ºC AA6063 AA6061 surface melting ( speed cracks ) 100 0 wt% Mg 2 Si 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 N. C. Parson et al. Extrusion Technology 1992, p13
Potential problems (2) Example of speed cracking, showing underlying re-melted eutectic colonies O. Reiso, Mat. Forum 28, p32 (2004)
3) Practical alloy development Brazing sheet is a clad aluminium rolled product widely used heat exchangers core typically AA3xxx, cladding typically Al-10%Si A very elegant product, with one small problem www.aluminium-brazing.com
Scrap What to do with the inevitable process scrap (ingot crops, edge trims, etc.)? The core and clad are metallurgically bonded: can t separate re-melted average composition typically : Al -1.4%Si -0.8%Mn-0.1%Mg this is x10 more Si than can be tolerated in most rolled products The more successful the sales of brazing sheet, the more scrap created Solution: register a new alloy designed to absorb the scrap: AA4015 typical application: low cost (painted) building sheet Only problem: mechanical properties rather poor cf. normal building sheet
(Blind?) Alloy development This is a cold rolled product, deriving its strength from a combination of work and solute hardening not feasible to increase cold rolling reductions (start and end gauges fixed) only option: increase level of solid solution Our client proposed increasing magnesium (and/or manganese) in the alloy (wrought metallurgists rule of thumb: if in doubt, increase Mg for work hardening) yield strength (MPa) 350 300 250 200 150 100 50 0 commercial reduction AA3004 AA4015 0 0.5 1 1.5 2 cold rolling strain The base alloy contains 0.1%Mg off line process used to investigate: 0.3% and 0.5%Mg hoping to close the gap
Mechanical properties Experimental alloys were cast up, homogenised, then hot and cold rolled The results were surprisingly disappointing 300 yield strength (MPa) 250 200 150 100 50 Rolled to a common final gauge (strain), all A4015 variants showed ~identical strength And exactly the same behaviour seen on making Mn additions 0 AA3004 AA4015 0.1Mg AA4015, 0.3Mg AA4015, 0.5Mg We were invited to consider whether the client s strategy made sense and could we explain why it was all going wrong?
The thermodynamic equilibrator melt melting casting homogenise hot roll treatment cold roll After homogenisation, slabs are hot rolled to ~ 3mm intermediate gauge For this client, the final 3 passes are coil to coil ~50% reductions, with many minutes between passes at ~350ºC On reflection, you would be hard pressed to find a process better designed to drive an alloy to equilibrium in the solid state!
Al-Mg-Si again The diagram shows the limit of solid solubility at 350ºC data taken from Phillips (1961) and Feufel et al. (1997) Increasing Mg in this alloy simply advanced into the 3 phase region at 350ºC with a Mg solid solution level pegged to the corner of the triangle 2.0 1.6 1.8 350ºC 1.4 1.2 1.0 0.8 0.6 0.4 0.2 Al-Mg 2 Si-Si H. Feufel et al, J. Alloys & Comp. 247, p31 (1997) Al 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 wt.% silicon
What else can we add? If Mn and Mg are ruled out because of the high Si in the alloy, what could we add (cheaply) that would be retained in solution? Cu was a candidate, provided the Mg level was also kept low (avoiding Q phase) potentially could retain e.g. 0.4-0.8 %Cu in solution 0.012 Al-0.1Mg-0.8Mn-1.4Si-0.8Cu 0.012 Al-0.2Mg-0.8Mn-1.4Si-0.8Cu mass fraction in FCC 0.010 0.008 0.006 0.004 0.002 Si Si Cu Cu Cu Si Mn Mg Mg 0.000 400 450 500 550 600 650 700 T/C mass fraction in FCC 0.010 0.008 0.006 0.004 0.002 Si Si Cu Cu Cu Si Mg Mg Mn Mg 0.000 400 450 500 550 600 650 700 T/C calculations undertaken by Chart Associates (2005)
Success? A series of alloys were cast based on AA4015 with Cu additions containing 0.3, 0.5 and 0.8 wt.% Cu For a fixed strain, 0.8% Cu alloy achieved ~75MPa strength increase in reasonable agreement with strain hardening prediction Yield Strength (MPa) 300 250 200 150 100 50 0 Measured measured predicted Predicted 0 0.3 0.5 0.8 Cu (wt %)
Strength ok, but corrosion? Not surprisingly, although Cu additions addressed the strength issue they also degraded the corrosion resistance of the product Not as much of an issue as might be expected: it is a coated product but would limit its application as a bare product 0% Cu 0.3% Cu 0.5% Cu 0.8% Cu corrosion test samples, 500 hours acidified salt spray (ASTM B287) (overlaid with image analysis of pitting corrosion)
Conclusions These application examples have been chosen to try and demonstrate the importance of setting phase equilibria predictions in a larger context There are times when thermodynamic equilibrium is achieved, either unavoidably or by design and other times when the process route has evolved to avoid equilibrium at all costs One of the most important application areas of phase equilibria relate to the provision of realistic local equilibrium boundary conditions increasingly required by microstructural kinetic models during processing Understandably there are gaps in the availability of reliable experimental data concerning metastable phase equilibria but some equilibrium data also very sparse for molten aluminium alloys e.g. relating to hydrogen in ternary or higher alloys e.g. interactions of molten salts with molten aluminium alloys (alkalis) e.g. solubility of carbon in molten aluminium, and precipitation of carbides