Part X - Communications - Formation of Dislocation Clusters During Sintering of Calcium Fluoride

ThIS note reports the observation of masses of dislocation etch pits around the weld necks of small single-crystal particles of calcium fluoride sintered to a cleaved face of a larger CaFz crystal. Crystal particles in the -50 +I00 mesh size range were placed on freshly cleaved CaFz surfaces and heated at 1250°C for 30 min in a tantalum container in an argon atmosphere. The sintered specimens were then etched at room temperature for 40 to 50 min in a 2 pct sulfamic acid solution which is a selective etch for dislocations in caF2.' Figs. 1 through 3 show the masses of dislocation etch pits observed around weld necks after etching. In some cases, particles were gone after removal of the specimens from the furnace although weld necks were readily visible. In other instances, no etch pits formed around a weld neck. A possible cause of concentrations of dislocations on the crystal surface is mechanical deformation of the base crystal when particles are dropped on it. If such a deformation does occur, it would be much smaller than that caused by the light punching of a crystal with a sharp instrument which results in large concentrations of etch pits. However, crystals deformed by punching with the sharp instrument and annealed at the conditions of these experiments (1250°C for 30 min) before etching showed no concentrations of dislocation etch pits. It is obvious that dislocations from the much smaller deformations, possibly created when particles are placed on the surface, would also anneal out. Etching of large crystals which had particles placed on them in the usual manner but which were not heated showed no dislocation concentrations such as shown in Fig. 1. The magnitude of dislocation etch-pit concentrations did not vary with extensive variation of the cooling rate. The appearance of many of the etch-pit clusters is typical of a well-annealed condition, indicating that the dislocation concentrations formed before the specimen temperature was lowered. Therefore, it is evident that thermal stresses in the neck area did not create the deformation indicated by the presence of the dislocations. The possibility exists that the etch-pit concentrations at places where particles had been removed may be the result of deformation accompanying the fracture of the sintered bond. That this is not so was demonstrated by breaking off particles around which no etch pits occurred. Re-etching never resulted in the large concentrations observed at sintering sites. The stress available to effect material movement during sintering of two particles will depend on the geometry at the contact point but can easily exceed the macroscopic yield stress in CaFz systems. It appears that the plastic deformation observed results from sintering or simply from the weight of the small particles. It has been previously argued that plastic flow makes an important contribution to the initial densification of oxides having the fluorite crystal structure.2p3 If plastic deformation occurs, it would begin as soon as the temperature is sufficiently high