Institute of Metals Division - Order-Disorder Transformation in Cu-Au Alloys near the Composition CuAu

Results of a Debye-Scherrer X-ray investigation are given which show that the order-disorder transformation is a first-order or heterogeneous reaction in Cu-AU alloys with compositions near CuAu. Evidence was found for conventional tie-line segregation across a usual type of two-phase field separating the ordered and disordered fields in the Cu-Au equilibrium phase diagram. The horizontal and vertical widths of the two-phase fields are about 3 atomic pct and 20°C, respectively, at 43 and 54 atomic pct Au. No evidence for the existence of an ordered structure based on a stoichiometric composition of Cu3Au2 could be found. ALTHOUGH the modern theories relating the de-Agree of order of binary alloys to temperature and composition have met with considerable success, the nature of the transformation from the disordered state to the ordered state and vice versa has never been well understood. It has been assumed by some' that this is a second-order transformation, that is, a homogeneous change of state. Others2 hold that the transformation is first-order and that the effects characteristic of heterogeneous phase transformation apply. Since this subject is discussed in detail in a recent paper,' the arguments will not be repeated here. The present paper summarizes an experiment which was designed to distinguish between these two viewpoints for the case of Cu-Au alloys near the composition CuAu. The Cu-Au system is an important one because it furnishes prototype alloys, the behavior of which has formed the basis of much of the present-day order-disorder theory. It has recently been shown- hat in alloys near Cu3Au there is a temperature range within which the ordered and disordered states coexist in equilibrium and are distinguishable as separate phases. Therefore, the transformation must be first-order for these alloys. A similar demonstration for alloys near CuAu, however, has been lacking. Experimental Method Essentially the experiment consisted of equilibrating Cu-Au samples at various temperatures, quenching them in water to retain the high temperature states, and then examining them at room temperature for the coexistence of the ordered and disordered structures. The thermal gradient method of heat treatment- as used because it was important that all temperatures over the transformation range should be represented in the test. Briefly, this method consisted of holding a wire of the desired composition, sealed under vacuum in Pyrex, in a known temperature gradient for a long enough time to allow each part of the wire to assume the crystal structure characteristic of the temperature at which it was held. The temperature gradient was produced by inserting into an ordinary wire-wound cylindrical laboratory furnace, an 18 in. length of 1/8 in. ID ceramic tube which was heavily wrapped with asbestos. The furnace power was controlled by a Tag-liabue Celectray controller and a chromel-alumel thermocouple with the junction located on the heating elements. During the equilibrating treatment the widest variation of temperature within the gradient tube was approximately 4°C at the highest temperature. The temperature at various places within the tube was determined, before inserting