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Atmosphere / Material Interaction Atmosphere / Material Interaction Powder Metallurgy Summer School 2016, EPMA, Valencia Christian Gierl-Mayer TU Wien Institute of Chemical Technology and Analytics What‘s the connection between sintering of PM-steels of composition Fe-C-xM-yM2 and the atmosphere? (Miba Sinter Austria GmbH) (Fe-4%Ni-2.5%Cu-0,5%Mo-0,5%C) Provocative statement: “OK, protecting gas is necessary, but we usually don‘t care much” Alloying Elements Pressing Aid Base Powder Mixing Shaping Soft Annealing Sintering Double-Press Post Treatment: Thermal Treatment, Calibration, joining, Impregnation, machining,… Finished Production scheme for PM process Part (after E.Mosca) Sintering: One possible definition: Thermal treatment where loose powder becomes densified and the desired composition. Driving force: Energy generated by the minimization of surfaces Heating period Isothermal sintering 1. Forming of contacts by diffusion processes Forming 2. Shrinkage: accelerated by higher of Densification contacts stage Final stage starting energy of the system (fine powder) e.g. MIM Liquid phases: e.g. HM Density Densification, 3. Final stage: desired microstructure is Temperature Time generate Schematic illustration of pressure less sintering solid state sintering (after W.Schatt) Metallic core Oxide layer Sintering of spheres Metallic (after W.Schatt) core Necessity to remove oxide layer diffusion between metallic structures forming of contacts Most important factor for Generation of Contacts: Degassing and deoxidation processes Principle: Metallic powders are thermodynamically unstable covered by Oxide layer on the surface Behaviour is described by Richardson Ellingham-diagram: Free Gibbs energy of the reaction n*M + y*1/2O2 MnOy* Metal + Oxygen metal oxide towards temperature Richardson-Ellingham-diagram for reduction with C (after A.R.Glassner) 6 Possible statement: Oxides of the usual alloying elements Ni, Cu, Mo are easier to reduce than the oxides of Fe This means: Describes the stability of oxide (= how difficult it is to reduce), shows if a metal can be oxidized It does not say if the reaction is really happening, for a given case also kinetic effects must be considered, e.g. passivation (see Al vs. Fe) Holds for wrought as well as for sintered metals Richardson-Ellingham-diagram for the reduction with C 7 (after A.R.Glassner) -10 TG und MS in Argon TG /% Ionenstrom *10 /A 4.0 m28 100.00 TG 3.5 99.95 3.0 2.5 Fe-0,5C 99.90 2.0 99.85 1.5 [1.1 1.0 [8] 99.80 200 400 600 800 1000 1200 Temperatur /°C TG /% Ionenstrom *10-9 /A 100.05 m28 1.2 TG 100.00 1.0 Fe-4Ni-1,5Cu- 99.95 0,5Mo-0,5C 99.90 0.8 99.85 0.6 99.80 [1.1 0.4 99.75 0.2 99.70 [8] 200 400 600 800 1000 1200 Temperatur /°C 8 TG /% Ionenstrom *10-9 /A TG und MS in H2 TG 100.00 1.000 m18 m28 0.900 99.95 0.800 0.700 99.90 Fe-0,5C 0.600 99.85 [7] 0.500 0.400 99.80 0.300 [2.1] [8] 0.200 99.75 200 400 600 800 1000 1200 Temperatur /°C TG /% Ionenstrom *10-9 /A 100.00 TG 3.0 m28 99.95 Fe-4Ni-1,5Cu- 2.5 0,5Mo-0,5C 99.90 [8] 99.85 m18 2.0 99.80 99.75 1.5 99.70 [1.1] 1.0 99.65 [7] 200 400 600 800 1000 1200 Temperatur /°C 9 Conclusion: • Thermodynamics of the reduction is important factor in the success story of these alloying elements • Desoxidation processes formation of sintering contacts are depending on the behaviour of iron, only little influence by the alloying elements • Low stability of their oxides Sintering is possible in almost all atmospheres, that are useful for sintering of carbon steels • Neutral atmospheres (N2, vacuum) or reducing atmospheres (N2-H2, endogas) with rather modest quality (dew point, Oxygen-content) can be used • No problems with open furnace concepts (belt furnaces) 10 Tasks of sintering atmospheres: 1. Protection of powder compacts against undesirable reactions (oxidation, decarburization, carburization, …) 2. Removing the products of desirable reactions (e.g. reduction of oxides, delubrication) 3. Controlled removal of undesirable elements / contaminants (e.g. reduction of oxides) 4. Controlled introduction of interstitials (C, N, B) Different degrees of reactivity : • Inert atmospheres (fulfil tasks 1 and 2) • Reactive atmospheres (fulfil tasks 1, 2, 3 and/or 4) Groups of sintering atmospheres (depending on reactivity) • Inert Atmospheres: Vacuum; • Oxidizing atmospheres: air, noble gases (Ar, He). H2O, CO2, occasionally CO; Caution: Never completely usually undesirable except for inert, traces of O2, N2, .. delubrication/binder burnout (Richard Kieffer: „There is (debinding of PIM Al in O2) reducing and oxidizing • Reducing atmospheres: H2, to vacuum“) some extent CO • Partly inert atmospheres: • Carburizing atmospheres: CO, Nitrogen (hardly any reaction C3H8, C2H2, endogas.. with steels, reaction with Cr in • Decarburizing atm.: H O, CO , stainless steels; strong 2 2 O , exogas reaction with Ti; formation of 2 AlN during sintering of Al alloys • Nitriding atmospheres: NH3 (forms nascent nitrogen), N2 in plasma Nitrogen: inert or reactive atmosphere? ASC 600MPa Ar TG /mg ASC Ar DTA /µV ASC 600MPa N 2 Inflexion point: 1180 .4 °C [6.1][6.1] ASC N2 22 Exo 0.2 20 Inflexion point: 1172.7 °C [3.1] 0.1 [1.1]18 [4.1] [2.1] 0.0 16 [8.1] [7.1] -0.1 14 12 -0.2 1000 1050 1100 1150 1200 1250 1300 1350 Temperature /°C TG/heating section of plain iron in different atmospheres: mass gain in the temperature range 1100 … 1200°C when sintering in N2 ASC 600MPa Ar DTA /µV ASC 600MPa N2 Peak: 861.0 °C ASC 600MPa vacuum -15 Exo Onset: 881.3 °C -20 -25 -30 -35 Peak: 882.9 °C -40 Peak: 872.9 °C Onset: 895.1 °C -45 Onset: 884°C -50 -55 800 820 840 860 880 900 920 940 Temperature /°C DTA/cooling section of plain iron in different atmospheres: shifting of austenite-ferrite transformation to lower T when sintering in N2 Gas volumes in the sintering atmosphere External (free) atmosphere: composition adjustable by the furnace operator (also with regard to O2, H2O content); affected also by the furnace type, design and gas tightness Transport through convection and diffusion Diffusion and Convection External atmosphere Diffusion Internal atmosphere Internal atmosphere: composition in part defined by reactions between atmosphere and solid body = local equilibria, in particular regarding content of H2O, CO, CO2 Transport through diffusion; convection through nonisothermal effects Boundary layer at the compact surface: transport through diffusion; convection only by „blowing“ of the pores, e.g. during heating, or „sucking“ during cooling Crucial period for reactions between atmosphere and compact: Heating section • Continuous change of temperature and thus shifting of equilibria: high temperature favours reduction and decarburization • Change of gas density in the pores gas flow from the pores into the free atmosphere • Most pronounced change of specific surface, which lowers the reactivity; on the other hand faster diffusion processes with increasing temperature • Dissolution reactions of alloy elements with matrix lowering of their chemical activity Most important interaction between powder compact and atmosphere: removal of oxides Virtually all metal powders bear oxygen; oxide layers on the surfaces essential in some case for safety reasons (Al powder; Carbonyl Fe) Oxide layers inhibit formation of stable sintering bridges, the more, the higher the stability of the oxides is Remedy: Reduction of the oxide layers in the early stages of sintering (heating stage); reduction either by components of the atmosphere (mostly H2) or by carbon present in the powder compact (sintered steels, hardmetals, ….) Reduction reactions for metal oxides: • MeO + H2 Me + H2O reduction with atmospheric constituent • MeO + CO Me + CO2 indirect carbothermic reduction (at low T) • MeO + C Me + CO direct carbothermic reduction (at high T) • MeO + Mf Me + MfO metallothermic reduction Conclusion (recapitulation): • Thermodynamics of the reduction is important factor in the success story of these alloying elements • Desoxidation processes formation of sintering contacts are depending on the behaviour of iron, only little influence by the alloying elements • Low stability of their oxides Sintering is possible in almost all atmospheres, that are useful for sintering of carbon steels • Neutral atmospheres (N2, vacuum) or reducing atmospheres (N2-H2, endogas) with rather modest quality (dew point, Oxygen-content) can be used Disadvantages of Ni, Cu, Mo: Expensive, massive price push in the last decade (Mo up to 30x) Ni – fine powder hazardous Alloying elements in wrought steels: Cr, Mn, V, Si Oxides much more stable than oxides of Iron Desoxidation of surface oxides not only dependant on the desoxidation of iron, but from alloying elements Richardson-Ellingham-diagram for reduction with C 19 (nach A.R.Glassner) Demands on furnace atmospheres: Alloying elements Fe-C; Mo, Cu, Ni: can be sintered in any atmospheres (no high demands) Alloying elements Cr, Mn, V: CO is oxidising at the usual temperatures (1120°C, belt furnaces) Criteria: pCO < pCOeq. 20%CO Equilibrium partial pressure of CO as function of the temperature for the carbothermal reduction of the oxides in Fe-C and Fe-3%Cr-C (after Danninger) Chromium as alloying element: Successfully introduced into the market 1998: Astaloy CrM with 3% Cr (+0,5%Mo), prealloyed; subsequently „Astaloy CrL“ (1.5%Cr-0.2%Mo); „Astaloy CrA“ (1.8%Cr) Why prealloyed? Cr can be sintered only at high temperatures and low dew points (if a = 1) Alloy Fe-3%Cr aCr = 0.025 purity requirements towards the atmosphere are somewhat lower (Lit. Arvidsson et al.) Astaloy CrM (SEM) 21 SE of surface of Cr-containing powders (by Hryha et.
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