The following is an outline of the main metallurgical process developments which have occurred at Port Pirie during more than 100 years of smelting. Emphasis is placed on those process developments which evolved from research and development at Port Pirie, rather than those based upon purchased or established technology and straightforward plant engineering. Most processes involved have undergone major change and improvement through the efforts of Port Pirie staff. A culture of metallurgical research and development evolved strongly during the years when G K Williams made such a great impact, and continued for half a century. This culture involved strong links with external research bodies, particularly universities. A near complete bibliography of these developments is provided, together with a listing of patents. Research and development by The Broken Hill Associated Smelters Pty Ltd commenced in 1918 at South Melbourne, and after transfer to Port Pirie in 1921, continued there until 1989. Three periods of highly successful innovation resulted - that of G K Williams into the 1930s, the post-war period until about 1962 and the period with developments led by Denby H Ward from about 1970 to 1985.