Wednesday, 12 March 2014

Annealing - Physical Changes

Physical changes of Glass at the Annealing Point

What happens at the annealing point and what is its relevance to compatibility? There are two main changes that occur – physical and chemical. They both affect the temperature of the annealing point, but in different ways. These notes are an attempt to understand these changes and how they affect compatibility.

The first requirement is to understand what the annealing point is. First it is a range of temperature during which the glass transforms from a liquid to a solid. It has a definition:

The annealing point is the point at which the material reaches the glass transition temperature. It occurs in a temperature region at a point where stresses can be relieved in a very short time. It is defined mathematically by a specific viscosity. In simple terms, this is the temperature below which viscosity prevents any further configurational changes.

Any contraction beyond the transition temperature range is due only to the lower kinetic energy of the groupings of the tetrahedra molecules. Thus, the compatibility of the glasses is determined at the annealing range as a combination of expansion/contraction and viscosity at the annealing range of temperatures rather than at the lower CoE which is more suited to crystalline solids. The transition temperature of a given “glass composition” depends both on its constituents and upon the rate of cooling.

The physical changes of glass during the transition/transformation range of temperatures are various:

  • Viscosity has a very large increase with temperature reduction, but without any discontinuity. Viscosity has an enormous effect on the activity of molecules in glass. As the glass cools below its transition temperature it causes the progressive immobility of the molecules.
  • The expansion rate (CoE) shows a relatively sudden change around the annealing temperature. Below the annealing point, the glass expansion and contraction behaves much like the CoE at the lower, measured temperatures. This means viscosity may be the most important element in creating a stable fusing compatible glass.
  • The amount of heat required to increase the glass temperature rises quickly rather than the previous regular heating rate needed to achieve unit changes.
  • The shear modulus changes rapidly, making the glass much more brittle below the annealing point.
  • The rate of heating or cooling can affect the exact temperature at which the glass transition point occurs.

The annealing phase (glass transition) is a dynamic process where time and temperature are to some extent exchangeable. This allows annealing to occur at the lower part of the range of the transition phase, but the glass then needs a slower cool from there. From the (higher) annealing point temperature - as defined by viscosity - the cool can be a little more rapid than at the lower temperature range of the transition phase. The anneal at the lower part of the transition saves annealing and cooling time for thick slabs, but for thinner pieces (less than 9mm), soaking at the annealing point and cooling from there is the simpler process.

Slow cooling results in a lower transition range because the tetrahedra forms of the molecules have more time to rearrange (to the degree that this is possible). This slower cooling results in tighter packing of tetrahedra as the mass reaches its transition range. When the glass reaches room temperature, its volume will be smaller when cooled slowly than glass melt which has been cooled rapidly. Hence, slower cooling from the melt results in a denser glass.