I recently had the opportunity to address a large group of materials scientists and engineers who work for Baker Hughes. I attended a few of their talks during the two-day conference and I was impressed with how complex and sophisticated the technologies involved are. While this blog is dedicated to reservoir issues I decided to share some of the things I learned about the history of some materials science research, some of the state-of-the-art and the people who make these advances. Reservoir engineers and other asset team members need to be aware of the technologies required to drill, complete, equip and produce hydrocarbons in a wide variety of environments. In this entry I will talk about the history of stainless steel, but I want to first look at the history of metal usage.
Copper (Cu) was probably the first metal used as a tool. Gold may have been used previously for decorative purposes and meteoric iron may have also had limited use as tools. Cu occurs naturally but sporadically in its unoxidized form and it began to be used locally in the 8,000-10,000 BCE period as the first farming villages appeared. By about 5,000 BCE copper was extracted with heat by potters from the ore they were using and by about 3500 BCE copper was being hardened with tin (Sn) to make bronze and could be useful for serious toolmaking. It is easier to work bronze than iron.
This is also about the time the first evidence of the use of iron (Fe) occurred. Most non-meteoric iron occurs in an oxidized form. Iron smelting to extract iron was developed in the 1500-1200 BCE time frame. Iron smelting requires higher temperatures than those needed to extract copper. Hittites developed a method to achieve these temperatures using charcoal. Iron became a big hit! The oxide was widely available; iron-carbon alloys were much harder and could produce more reliable tools and edges that could be sharpened. Fe has important advantages over Cu: It is much more common and cheaper. The Hittite kings tried to keep this knowledge secret—iron smelting may well have been the first great industrial secret.
The secret couldn't be kept long and its use spread widely. One iron axe could cut down enough wood for dozens of homes and soon much of populated Europe was deforested. By 1200 BCE, real steels were developed using quenching and hardening techniques. The Greeks made sophisticated alloys of iron and carbon; they developed methods to quench and temper steel to harden it. Homer refers to the tempering of steel in the Odyssey.
By 900 BCE, hardened steel tools were in widespread use and the bronze age drew to an end. But iron tools all shared something in common. They rusted. We have few examples of early iron tools because they have largely oxidized away. Early examples of “stainless” steels included:
• Chinese Qin Dynasty (3000 BCE) advances in which Chromium (Cr) was used to strengthen them and protect them from corrosion.
• The Iron pillar of Delhi (400 BCE) is a 7.3 meter tall forge welded column with a high Phosphorous (P) content.
Wootz steel was developed before 300 BCE. By 1200, Damascus steel swords from the Middle East acquire nearly mythical status. Steel making remains a slow, painstaking manufacturing process until Benjamin Huntsman discovered the crucible casting methods giving rise to the steel making center near Sheffield, England.
The 18th century saw the discovery of elemental Nickel, Molybdenum, Chromium and more. These would lead to advanced types of steel. French scientist Pierre Berthier recognized the corrosion resistance of Fe-Cr alloys as early as 1821; Leon Gillet documented the constitution of what we would recognize as stainless steel in 1904. Philip Monnartz of Germany described the corrosion resistance of stainless steel and in 1912, Eduard Maurer and Benno Strauss of Germany's Krupp Iron Works, patented the first austenitic* stainless steel of a 21% chromium and 7% nickel combination. The Krupp Iron Works company built a 366-ton sailing yacht with a Ni-Cr steel hull in 1908. With its 40-man crew, the Germania found itself in England at the outbreak of WW I and was captured as the “spoils of war”. It would have a fascinating future including a stint as a floating dance hall/restaurant near Miami before reaching its watery grave near Key Biscayne, Florida where recreational divers can see it.
Harry Brearley is often credited with inventing stainless steel. In 1907 he lead the Brown-Firth Research Lab in Sheffield, England. Investigating ways to develop rust proof gun barrels, Brearley noticed that some Cr alloy waste steel was not rusting. He patented the first martensitic* stainless in 1913. Brearley wasted no time trying to market this invention, as Sheffield was home to England's main cutlery manufacturers. He struggled with acceptance and was once known as the inventor of the “knife that would not cut”.
Brearley left Firth over an ownership dispute of the stainless steel invention. He came to America only to find that Elwood Haynes had a pending patent on martensitic stainless steel that would not be granted until 1919. They joined forces to develop the American Stainless Steel Corporation. European firms added Ni and other materials to stainless steel and the technology advanced rapidly. By the 1920s, new alloys were being used as surgical implants and industrial tanks. The rest “is history.”
In our next entry we will examine some Baker Hughes materials inventions. Specifically we will see how an advance in nanotechnology allows operators to apply the multistage technologies developed for unconventionals to sand control applications. These technologies will allow much higher productivities without conventional sand control screens or frac packs!