Spontaneous nucleation temperatures

Different methods can be implemented for triggering the nucleation process and reducing the effect of the rather broad distribution of spontaneous nucleation temperature whitdi is one of the main causes of vial-to-vial variation of ice morphology and, consequently, of the distribution of drying times and of distributed morphology parameters in the freeze-dried product. 

Under equiUbrium vapor pressure of water, the crystalline tfihydroxides, Al(OH)2 convert to oxide—hydroxides at above 100°C (9,10). Below 280°—300°C, boehmite is the prevailing phase, unless diaspore seed is present. Although spontaneous nucleation of diaspore requires temperatures in excess of 300 °C and 20 MPa (200 bar) pressure, growth on seed crystals occurs at temperatures as low as 180 °C. For this reason it has been suggested that boehmite is the metastable phase although its formation is kinetically favored at lower temperatures and pressures. The ultimate conversion of the hydroxides to comndum [1302-74-5] AI2O2, the final oxide form, occurs above 360°C and 20 MPa. 

TBP and injected into a hot ( 350 °C) solution of TOPO (12 g). The injection of CdSe precursors into the hot solution ofTOPO resulted in spontaneous nucleation of CdSe nanocrystals and a decrease in temperature. Once the temperature was stabilized, an additional amount (0.4 mL) of the precursor solution was added for the growth of the nucleated nanocrystals. Here, Ostwald ripening was avoided by separating the nucleation and growth processes. All the reagents and the reaction were kept under an Ar atmosphere to avoid fire hazard and surface oxidation of the nanocrystals. 

Polymer-protected, monodisperse, nanoscale silver particles (Fig. 9.2.1c and d) have been obtained through spontaneous nucleation by the polyol process as follows (23). PVP (1-25 g) and AgNOj (50-3200 mg) were dissolved in EG (75 mL) at room temperature. Then the solution was heated up to 120°C at a constant... 

It can precipitate as potassium hydrogen tartrate (KHT) or as calcium tartrate (CaT), the latter being practically insoluble in aqueous solutions. Their equilibrium solubility varies with temperature, pH, and alcohol content, while the presence of a few wine components, such as polysaccharides and mannoproteins, may hinder spontaneous nucleation even if the solution is supersaturated. From Figure 14 that shows the equilibrium tartaric acid-dissociated fractions versus pH and ethanol volumetric fraction (Berta, 1993 Usseglio-Tomasset and Bosia, 1978), it can be seen that in the typical pH range (3 4) of wines KHT is predominant. As temperature is reduced from 20 to 0°C, KHT solubility in water or in a 12% (v/v) hydro-alcoholic solution reduces from 5.11 to 2.45 kg/m3 or from 2.75 to 1.1 kg/m3, respectively (Berta, 1993). Each of these data also varies with pH and reaches a minimum at the pH value associated with the maximum concentration of the hydrogen tartrate anions. For the above-mentioned solutions, the solubility minimum shifts from pH 3.57 to pH 3.73 as the ethanol content increases from 0 to 12% (v/v) (Berta, 1993). 

Any general increase in supersaturation, brought about by increasing concentration or decreasing temperature, raises the local metastable potential and smoothes away the potential barrier to spontaneous nucleation, shown... 

The nucleation temperature, which exceeds the boiling point of the species, is the temperature at which bubbles spontaneously appear in the liquid. Bubble nucleation is a rate process, and its description on the basis of a nucleation temperature is a simplification. Homogeneous nucleation temperatures are substantially above the boiling point heterogeneous nucleation—aided, for example, by impurities like dust—may occur at somewhat lower temperatures that nevertheless still exceed the boiling point. 

The concentration versus temperature curve shown in Figure 7 shows the hypothetical scenario in which supersaturation is created by cooling. When a solution represented by point A is cooled without the loss of solvent (line ABC), spontaneous nucleation will occur, when conditions corresponding to point C are attained. The boundary between the solubility line (solid line) and the line (points B to C) at which spontaneously nucleation occurs is referred to as the metastable zone. When the metastabe zone is exceeded, the nucleation rate increases rapidly, and the crystallization process becomes uncontrolled. Within the metastable zone, the nucleation rate is slower such that control over the crystallization process may be achieved. Nucleation may also be facilitated within the metastable zone by the addition of crystalline seeds of the solute of interest (i.e. secondary nucleation). 

Figure 7. Concentration versus temperature curve for a hypothetical system in which supersaturation is created by cooling. The solid line represents the solubility curve, the dashed line represents the point of spontaneous nucleation. The region between these two lines is the metastable zone. Adapted from Rodriguez-Hornedo (1991).

---