Development of Permanent Record Papers

by William K. Wilson

William K. Wilson earned his M.S. in chemistry from West Virginia University. He has thirty-eight years of experience in paper research at the National Bureau of Standards (National Institute of Standards and Technology). He has been a guest worker at the National Archives and Records Administration. Most of his publications are on 1) the effect of light on paper, 2) the stability of cellulose acetate films, 3) accelerated aging of paper under various conditions, and 4) work with ASTM on the development of guidelines and specifications for paper for permanent records.
Condensed from "Some Happenings on the Way to the Development of Permanent Record Materials," by William K. Wilson, p. 51-55, Preservation Research and Development: Round Table Proceedings, September 28-29, 1992. Washington: Library of Congress, Preservation Directorate (June 1993).

There are many ways a historical paper of this nature would be written, and this one is arranged by time periods. The progress in earlier times may seem somewhat juvenile, but we must remember that the invention of the wheel, which we take for granted, was a giant step forward.

Before 1900

We certainly should make a bow to Emil Fischer, the Nobel prize winner who determined the structures of the sugars, especially glucose. This work was required as a basis on which cellulose chemistry could build. It is questionable whether Fischer had any idea at the time of the importance of his work to cellulose chemistry--in the twenties the greats were arguing violently over the existence of polymers.

We also must list Arrhenius in this time frame. His classic paper, published in 1889 (1), discussed for 23 pages the inversion of raw sugar by acids, and on one page he gives his famous formula showing the relationship between reaction rate, temperature and activation energy. Although he is known the world over for his famous "Arrhenius Plots," it is ironical that not a single plot appears on any of the 23 pages. It should be noted in passing that Arrhenius developed the theory of ionization for his doctoral thesis. His major professor and his examining committee were so unimpressed that he just barely got his degree. The examining committee is forgotten, but Arrhenius is known to every chemist the world over.

1900-1930

Smith (2) gives an excellent account of the history of records deterioration, especially before 1900, and Wilson (3) provides a history of records research at the National Bureau of Standards. Thomas (4) describes the history of alkaline papermaking up to about 1969. Kantrowitz, et al. (5) provided a bibliography on permanence and durability from 1885 to 1939, and Luner (6) published an excellent article on paper permanence covering the literature up to 1969.

The good news in 1901, although practically no one knew it, was making paper with an alkaline filler. This was the handiwork of Edwin Sutermeister (4). Although he knew what he was doing, the real reason for doing it was that his boss told him to do something about the huge pile of by-product calcium carbonate in the back yard of the mill. Sutermeister set aside some samples for storage and, as of about 10 years ago, these samples were still in good shape.

In 1925 Gösta Hall of the Royal Technical University of Sweden spent a month in the Paper Section at the National Bureau of Standards (NBS). Having just completed a project in Sweden on the permanence of paper, he was of great assistance to NBS scientists, and he influenced the direction of records research for many years. Dr. Hall showed that alum was bad for stability of paper. Nothing new, but he provided quantitative data. He developed a method for determining the acidity of paper. These tests are TAPPI standards today.

In the late twenties a research program was initiated in the NBS Paper Section on stability of records, and this program was active until WWII. It was initiated by the American Library Association, the Carnegie Foundation, and the National Research Council. In the early thirties the National Archives joined the list of sponsors.

1930-1950

The above program was very extensive for the time, and the following results were obtained:

Papers containing rosin-alum could be very stable toward accelerated aging if no excess alum were used. An excess of alum produced unstable paper.
Papers made with a calcium carbonate filler were very stable, but no more than the above rosin-sized papers with a minimum of alum.
Two programs were started on comparison of accelerated aging with natural aging. These programs would later show that aging for three days at 100°C in a dry oven correlated fairly well with natural aging. However, it was obvious that the prediction of stability by accelerated aging was not an exact science. They also showed that rosin sized papers were very stable if not quite enough alum was added to react with the rosin, and that papers containing a calcium carbonate filler were very stable.
The deleterious effects of sulfur dioxide were demonstrated, and a procedure was developed for removing sulfur dioxide from library air.
From a study of the effect of light on paper, Launer (7) showed that: a) paper is bleached by light, if irradiated without heat; b) the principal reaction(s) is photo-oxidation--oxygen is necessary for the reaction to occur; c) a post-irradiation effect occurs in which the paper is bleached during irradiation, and darkens in dark storage, an effect that today would be discussed in terms of trapped free radicals; d) newsprint is bleached by light in the absence of oxygen; e) newsprint is greatly stabilized against photo-oxidation by impregnation with sodium bicarbonate.

Hanson (8), while a graduate student at the Institute of Paper Chemistry, examined a book dated 1576 in which the signatures (sections) were printed on different kinds of paper. They varied from discolored and weak to white and strong. It was found that the white, strong sheets contained about two percent calcium carbonate.

In the late thirties, load-elongation was performed with a balance arrangement to measure load and with an optical setup to measure elongation. Ten years later, with the spurt in electronic instrumentation motivated by the war, load-elongation was performed with a recording load-elongation instrument. This was real progress, for elongation and tensile energy absorption are important parameters in the aging of paper.

1950-1970

These two decades saw a real awakening in records research, and several laboratories were created. Previously, records institutions did not have inhouse research facilities but contracted research to scientific institutions. This period saw the creation of the research laboratory of the Library of Congress, directed by Frazer Poole; the research center at Carnegie Mellon University, headed by Robert Feller; and the Barrow Research Laboratory in collaboration with the Virginia State Library.

Gray (10) used Arrhenius plots in a study of the applicability of TAPPI Standard 453, "Effect of Dry Heat on Properties of Paper," to predict the relative stability of papers. Wilson used the Arrhenius approach in evaluating the stability of cellulose acetate films.

This period saw the beginnings of the use of other aging conditions for paper besides dry heat. Wilson (11, 12) used 90°C, 50% relative humidity in the aging of several papers. The Library of Congress also used 90°C, 50% relative humidity.

In 1966 the National Archives contracted with the Paper Section of NBS to develop specifications for permanent record papers. This project was to last more than 10 years. Part of the work was contracted to the New York State College of Forestry, and it was there that Cardwell (13) found that the cycling of temperature and relative humidity was more damaging to paper than a constant temperature and relative humidity.

During this work, four specifications for permanent record paper were developed and became ASTM standards: Bond and ledger paper, Manifold paper, File folders, and Copies from office copying machines.

1970-Present

If the period 1950-1970 was the awakening of records research, the time after 1970 was the explosion. The National Archives continued, intermittently, to contract research with NBS, but created its own laboratory in 1976. The Smithsonian Institution created the Conservation Analytical Laboratory. The Preservation Research and Testing Office at the Library of Congress and the Carnegie Mellon Institute developed substantial research programs, and the Getty Conservation Institute in Marina del Rey developed a research program for museums and archives.

Laboratories abroad include the Canadian Conservation Institute (Helen Burgess) in Ottawa, Canada; the Department of Conservation of the British Museum (Vincent Daniels) in London; the Department of Paper Science (Derek Priest) at the University of Manchester, Institute of Science and Technology, England; Centre de Recherches sur la Conservation des Documents Graphiques (Françoise Flieder) in Paris; and Istituto di Patologia del Libro (Carlo Federici) in Rome. And finally, the Central Research Laboratory (Judith Hofenk de Graaff) in Amsterdam and Riksarkivet, the national archives of Sweden (Ingmar Fröjd, coordinator) are carrying out some important work on the aging of paper and the effect of air pollutants on paper.

Graminski (14) and Du Plooy (15) systematically studied the degradation of paper at various temperatures and relative humidity values. For the first time, one could look at the broad picture of the effects of temperature and relative humidity on the degradation of paper. Paper degrades about twice as fast at 50% relative humidity as at 25%.

In order to assess the effect of change in temperature on degradation, one must have an idea of the activation energy of the degradation reaction. Erhardt (16) has discussed this; the activation energy is a measure of the energy "hump" which must be gotten over for the reaction to occur. The higher this energy barrier, the slower the reaction (all other things being equal). However, the higher the activation energy, the more sensitive the reaction is to changes in temperature.

A problem that has surfaced in the last couple of years is the attempt of makers of high yield pulp, which contains lignin, to include these pulps in the stock of papers meant for permanent records. Studies have shown that papers containing high yield pulps and a filler of calcium carbonate, except for discoloration, are stable toward accelerated aging. It will take a substantial research program to resolve the problem of discoloration.

References

1. Arrhenius, Svante. "Über die Reaktionsgeschwindigkeit bei der Inversion von Rohzucker durch Säuren." Zeitschrift für Physikalische Chemie 226-248 (1889).

2. Smith, Richard D. "Paper Impermanence: pH and Storage Conditions." Library Quarterly 39 (2): 153-195 (1969).

3. Wilson, William K. and Parks, Edwin J. "Historical Survey of Research at the National Bureau of Standards and Materials for Archival Records." Restaurator 5 (3/4): 191-241 (1983).

4. Thomas, Joseph J. "Alkaline Printing Papers." Library Quarterly 40 (1): 99-107 (Jan. 1970).

5. Kantrowitz, Morris S., Spencer, Ernest W. and Simmons, Robert H. Permanence and Durability of Paper: Annotated Bibliography of the Technical Literature from 1885 A.D. to 1939 A.D. Washington: U.S. Government Printing Office, 1940.

6. Luner, Philip. "Paper Permanence." Tappi Journal 52 (5): 796-805 (May 1969).

7. Launer, Herbert F. and Wilson, William K. "Photochemical Stability of Papers." Journal of Research of the National Bureau of Science 30 (1): 55-74 (Jan. 1943).

8. Hanson, Fred S. "Resistance of Paper to Natural Aging." Paper Industry and Paper World 20 (11): 1157-1163 (Feb. 1939).

9. Steiger, Fred H. "The Arrhenius Equation in Accelerated Aging Studies." American Dyestuff Reporter 47 (9): 2870290 (May 5, 1958).

10. Gray, Glen G. "An Accelerated-Aging Study Comparing Kinetic Rates vs. TAPPI Standard 453." Tappi Journal 52 (2): 325-334 (Feb. 1969).

11. Wilson, William K. and Hebert, Raymond L. "Evaluation of the Stability of Record Papers." Tappi Journal 52 (8): 1523-1529 (Aug. 1969).

12. Wilson, William K. and Hebert, Raymond L. "Evaluation of the Stability of Manifold Papers." Tappi Journal 55 (4): 1103-1107 (July 1972).

13. Cardwell, Robert D. Aging of Paper. Ph.D. dissertation, New York State College of Forestry, Syracuse, N.Y., 1973, p.A2-A4.

14. Graminski, E.L. "The Effects of Temperature and Moisture on the Accelerated Aging of Paper." In Durability of Macromolecular Materials, edited by R.K. Eby. (ACS Symposium Series, no. 95) Washington, American Chemical Society, 1979.

15. Du Plooy, Adriaan B.J. "Influence of Moisture Content and Temperature on the Aging of Paper." APPITA Journal 34 (4) (Jan. 1981).

16. Erhardt, David. "Relationship of Reaction Rates to Temperature." Abbey Newsletter 13 (3): 38-39 (June 1989).

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