Crystallization and phase transformation behaviour of electroless nickel-phosphorus deposits with low and medium phosphorus contents under continuous heating

Electroless nickel-phosphorus deposits with 5-8 wt% P and 3-5 wt% P were analysed for the effects of continuous heating on the crystallization kinetics and phase transformation behaviour of the deposits. The as-deposited coatings consist of a mixture of amorphous and microcrystalline nickel phases, featuring in their X-ray diffraction patterns. Continuous heating processes to 300C-800C at 20C/min were carried out on the deposits in a differential scanning calorimetric apparatus. The subsequent X-ray diffraction analyses show that the sequence of phase transformation process was: amorphous phase + microcrystalline nickel, f.c.c. nickel + Ni3P stable phases. Preferred orientation of nickel {200} plane developed in the deposits after the heating processes. Differential scanning calorimetry of the deposits indicates that the crystallization temperatures increased with decreasing phosphorus content, and increasing heating rate. Crystallization activation energies of the deposits (230 and 322 kJ/mol, respectively) were calculated using the peak temperatures of crystallization process, from the differential scanning calorimetric curves at the heating rates ranging from 5 to 50C/min. It was found that the deposit with lower phosphorus content has higher activation energy.

A reactive force field simulation of liquid-liquid phase transitions in phosphorus

A force field model of phosphorus has been developed based on density functional (DF) computations and experimental results, covering low energy forms of local tetrahedral symmetry and more compact (simple cubic) structures that arise with increasing pressure. Rules tailored to DF data for the addition, deletion, and exchange of covalent bonds allow the system to adapt the bonding configuration to the thermodynamic state. Monte Carlo simulations in the N-P-T ensemble show that the molecular (P-4) liquid phase, stable at low pressure P and relatively low temperature T, transforms to a polymeric (gel) state on increasing either P or T. These phase changes are observed in recent experiments at similar thermodynamic conditions, as shown by the close agreement of computed and measured structure factors in the molecular and polymer phases. The polymeric phase obtained by increasing pressure has a dominant simple cubic character, while the polymer obtained by raising T at moderate pressure is tetrahedral. Comparison with DF results suggests that the latter is a semiconductor, while the cubic form is metallic. The simulations show that the T-induced polymerization is due to the entropy of the configuration of covalent bonds, as in the polymerization transition in sulfur. The transition observed with increasing P is the continuation at high T of the black P to arsenic (A17) structure observed in the solid state, and also corresponds to a semiconductor to metal transition. (C) 2004 American Institute of Physics.