Microstructure and embrittlement of leaded copper alloys

Mechanisms responsible for the embrittlement of leaded "free-machining" copper alloys at intermediate temperatures (i.e. around 400 °C) are examined using a combination of microstructural and mechanical characterization. Tensile tests are conducted on pure copper and on industrial high-strength Cu-Ni-Sn alloys, comparing leaded and unleaded versions, at strain rates ranging from 10-4 to 10 s-1, and various temperatures between 25 °C and 800 °C. It is found that, in the leaded samples, both liquid metal embrittlement and grain boundary embrittlement operate at intermediate temperature,i.e., near the melting point of lead. Their respective importance depends mainly on the strain rate: fracture at high strain rate (10 s-1) displays characteristic signatures of liquid metal embrittlement, while at low strain rate (10-4 s-1) the ductility trough behaviour can be attributed to grain boundary embrittlement. In leaded copper and copper alloys, lead is mostly present as discrete inclusions, frequently located along grain boundaries. The dihedral angle of intergranular lead inclusions is then the main microstructural parameter besides their size. A new technique is proposed and demonstrated for the measurement of inclusion dihedral angle in a high-purity Cu-1 wt.% Pb alloy, based on room temperature characterization of samples that were held at elevated temperature at times sufficiently long for shape equilibration of the inclusions and then rapidly quenched. Quantitative scanning electron microscopic analysis of metallographic surfaces along which individual inclusions have been dissolved is used to deduce the dihedral angle using a mathematical fit of their solid/liquid interface. For a specific temperature, we show that the dihedral angle is not unique; this reflects the fact that high-angle grain boundary energies are not constant in copper. Existing micromechanical analyses of shape equilibrium for intergranular inclusions in the presence of external stress are adapted to produce an improved description at low stress and to take into account the inclusion bulk compressibility. The derivation is based on minimization of the global capillary and elastic strain energy associated with such inclusions. An adimensional parameter that depends on the applied stress, the inclusion volume, the elastic properties of the solid, and the relevant interfacial energies emerges from the analysis as the sole factor governing the shape of the inclusion. If void nucleation occurs easily within the inclusion, such that its apparent bulk modulus is nil, the inclusion become unstable, degenerating to a crack when this adimensional parameter exceeds a critical value. Measurements of the dihedral angle on samples previously subjected to a remote stress at 400 °C show that applied stress causes a reduction in the apparent dihedral angle of liquid lead inclusions. Calculated critical stresses for both leaded pure copper and leaded copper-nickel-tin alloys that fail at high strain rate by liquid metal embrittlement are calculated for individual inclusions in the metal. These calculated critical stresses correlate relatively well with the measured fracture stress, suggesting that shape instability of the inclusions cause fracture of the alloys. This result is applied towards the suggestion of general strategies for reduction of the susceptibility of leaded copper alloys to liquid metal embrittlement. A case study addressing the problem of quench cracking of leaded Cu-Ni-Sn alloys on the basis of experimentation and finite element thermomechanical simulation, showing how the problem can be alleviated in production, concludes the thesis.