As early as the 18th century, M.H. Klaproth, who later became Berlin's first chemistry professor, experimented on some ancient objects, principally coins. The most common analytical methods available then and still in use up to the start of this century were those which involved the use of solutions. The work of E. von Bibra deserves acknowledgement; in 1869, he compiled most of the previously known methods, and included many of his own. Although the answers to many archaeological queries were sought at this early stage with the available methods, little other than the definition of copper alloys was discovered. The introduction of physical methods, from the mid-20th century onwards, helped make studies more comprehensive. The work done by the groups of Sangmeister and Craddock have laid a sound foundation for the further use of natural science techniques in archaeological studies.