Abstract
Although the microstructure of carbon black has been under investigation for more than fifty years, there are still many aspects which are controversial and some which are virtually unexplored. The inherently low degree of crystallinity and the finely-divided state of carbon blacks have greatly hindered efforts to understand them. The purpose of this article is to cite the principal contributors to our understanding of carbon black microstructure, to discuss the significance of their contribution, to present a clear picture of the present state of our knowledge, and to note areas where controversy exists and where our knowledge is incomplete. The scope of this article is necessarily limited to a reasonably complete treatment of the several aspects of carbon black microstructure; that is, the arrangement of carbon atoms to form graphite layer planes, the arrangement of layer planes to form crystallites, and the arrangement of crystallites to form the more familiar carbon black “particles” or aggregates. Particular attention is paid to more recent articles and those which have shaped our thinking on carbon black microstructure. This article also includes a fairly complete review of various studies on the changes in microstructure which are brought about by heat treatment or oxidation. In general, the rather large number of studies reporting on the microstructure of other forms of carbon have not been reviewed (except for the work of Franklin whose contribution to our understanding of carbon-black microstructure is so immense that it must be included). Although gross, morphological features such as particle size, primary aggregate size and shape are studied briefly in order to relate them to microstructure, no effort was made to review comprehensively the body of literature pertinent to this subject. Also porosity and surface characteristics per se (as measured by gas adsorption techniques) are not treated in detail here. Rather than review a dreary list of papers which have only the slightest bearing on carbon black, the author has taken the liberty of dividing the articles reviewed into two categories. The first category, which is reviewed in some detail, includes those publications in which an important contribution was made to the understanding of carbon-black microstructure. The second category includes all those articles which are discussed only briefly or not at all because the authors have reported superficial or routine studies or they (probably unknown to them) have essentially duplicated the work of an earlier worker, or have reported uncorrected results which are thus so inaccurate as to be without real value to this article; or because they comprise work which is only peripherally related to carbon black microstructure. Also, references taken from other papers, but not reviewed here, are included in the latter category. Articles by Warren, Hofmann and Wilm, Steward and Cook and Walker contain bibliographies which will be helpful to those interested in the earlier work or in the microstructure of carbons other than carbon black. For the reader whose time is limited, an adequate picture of current understanding of carbon black microstructure can be gained by reading Sections II, IV, and V which are relatively short. Finally, a word about the spirit in which the review was written. At the request of the late Dr. Craig, a critical review was prepared in which every effort was made to point out shortcomings as well as classic contributions contained in the pertinent literature. Where the experts have disagreed, the reviewer, often with skill unequal to the task, has attempted to decide which one was the more correct in the light of current knowledge. It is with deep humility and great respect for those who have gone before that this review is submitted.