Published in The Picking Table 35(2), 6-11 (1994).

FAMOUS GRAPHITE CRYSTALS
FROM STERLING HILL, NEW JERSEY

John A. Jaszczak
Department of Physics and the Seaman Mineral Museum
Michigan Technological University
1400 Townsend Dr.
Houghton, Michigan 49931-1295

In 1941, Charles Palache published an important paper on the morphology of graphite crystals from Sterling Hill. One of his graphite crystal drawings, which has been reproduced in many publications, is drawn down the c-axis and gives the impression of being tabular. However, the given Miller indices indicate that the crystal was actually barrel-shaped, a rare morphology for graphite.


INTRODUCTION

In 1941, Charles Palache of Harvard University published a paper [hereafter referred to as CP41] titled, Contributions to the Mineralogy of Sterling Hill, New Jersey: Morphology of Graphite, Arsenopyrite, Pyrite, and Arsenic" in The American Mineralogist. The morphology of graphite was the focus of the paper, although the other listed minerals are illustrated and discussed to a minor degree. Historically, the symmetry of graphite had been the subject of some controversy. By goniometric measurements of the crystals from Sterling Hill, Palache correctly concluded that graphite is hexagonal with full symmetry.

CP41 has since been cited in at least 29 articles and books in the fields of mineralogy, physics, metallurgy and materials science, and includes publications in German, Russian and English (see Appendix). The paper contains five crystal drawings of Sterling Hill graphite, one of Ticonderoga, New York graphite, four of Sterling Hill arsenopyrite, and one of Sterling Hill native arsenic. Two of the graphite crystal drawings have since been reproduced in other publications. Those of the Ticonderoga crystal (CP41 fig. 5) and one of the Sterling Hill crystals (CP41 fig. 3; see fig. 1 of this paper) appeared in the seventh edition of Dana's System of Mineralogy, which Palache co-authored (Palache, et al. 1944). Reproduction of the figures in Dana's System has probably contributed greatly to Palache's drawings being widely regarded as the "textbook" examples of graphite crystals. Along with a sketch of a synthetic, scroll-type, whisker crystal of graphite, fig. 3 of CP41 also appeared on the cover of the book Preparation and Properties of Solid State Materials, vol. 4. (Wilcox, 1979). It was again reproduced, along with fig. 5 of the Ticonderoga crystal, in the book's first chapter on "Graphite Crystallization", written by I. Minkoff. In the book The Physical Metallurgy of Cast Iron by Minkoff (1983), fig. 5 of the Ticonderoga, NY crystal was included once more, but fig. 3 of the Sterling Hill graphite was not.



Fig. 1. Crystal drawing of graphite from Sterling Hill, NJ, which appeared originally as fig. 3 in Palache's 1941 paper in American Mineralogist. The crystal shows the basal pinacoid c{0001}, the first-order dipyramid p{10-11} and the second-order dipyramid phi{11-22}. (Drawing recreated using the computer program SHAPE.)





GRAPHITE CRYSTALS

According to Palache, the source of the studied crystals was Mr. Lawson H. Bauer of Franklin, New Jersey, who found and carefully isolated the graphite crystals from a coarsely crystalline marble impregnated with graphite, arsenic, realgar, pyrite, arsenopyrite, diopside and either stibnite or a lead sulphantimonide [probably zinkenite (Kolic and Sanford, 1993)]; the specimens were collected May, 1937 from the 900-foot level of the mine at Sterling Hill. Dilute hydrochloric acid was used to separate these minerals in abundance from the marble matrix. In 1937 and in following years Bauer made contributions of isolated graphite crystals to the Harvard Mineralogical Laboratory. Mr. Bauer is said to have been a generous, careful and patient enthusiast of Franklin minerals who at one time became very fond of graphite (J. L. Baum, personal communication, 1993; Frondel, 1955).

Overall, the graphite crystals described by Palache in CP41 are considered to have been of superior quality. For example, experts in the laboratory synthesis of synthetic graphite crystals (Austerman, et al., 1967) stated: The natural crystals described by Palache are the highest quality crystals reported in the literature as far as the authors are aware, and his description serves as a point of reference for the graphite crystals grown in the laboratory.

Palache described the Sterling Hill graphite crystals as being up to 1 or 2 mm in diameter, while the best crystals did not exceed 0.5 mm. Although hundreds of graphite crystals were examined by him, only ten were completely measured by optical goniometry. From these 10 crystals, Palache listed 15 sets of measured angles corresponding to 16 different crystal forms (see table 1). Palache noted that most of the crystals had been distorted as a result of tectonic deformation, which caused mechanical twinning of both the graphite and the surrounding calcite. Few graphite crystals remained undistortied or showed only a single twin lamella.

TABLE 1: Graphite crystal forms measured by Palache (1941) from a set of 10 crystals from Sterling Hill, NJ. The basal pinacoid {0001} was used for alignment of the crystals on the goniometer and was not included in table 1 of CP41. Presumably at least one {0001} faced existed on each of the 10 crystals.

The most common form observed by Palache on graphite crystals from Sterling Hill was the basal pinacoid {0001}, which he described as dominant and highly lustrous. The same form is the most common in graphite form almost all other localities woldwide. After that, the first order dipyramids {10-11} and {10-12}, which determined the hexagonal outline of the crystals, were about equally as common. The {10-13} dipyramid was slightly less common, and other dipyramids less common still. Palache noted that only rarely did any one of the dipyramids show all 6 faces on (the top half of) a crystal, and the zone of these faces was often completely striated. The first order prism {10-10} was rarely more than a line face, always rough when present, but often missing altogether. Second order dipyramids, such as {11-22}, occurred as small faces such as truncations of first order dipyramid faces. It is noteworthy that none of the forms listed by Palache corresponds to a general form {hkil} (were h, k, and l are non-zero and have no special relationship to one another), as general forms of graphite not been well-documented in subsequent literature either. Palache did note, however, the existence of crystal faces which were not in the dominant zones and could not be simply indexed.



Fig. 2. (a) Same crystal as in fig. 1 but rotated to a different viewing orientation using SHAPE. (b) Cleaved version of (a) which also appears like fig. 1 when viewed down the c axis, but is more apt to fit Palache's description of the original crystal.



Graphite usually forms tabular crystals, when it forms good crystals at all. Of the crystal drawings of graphite in Palache's paper, two showed the crystals from an inclined view and clearly are tabular. Palache indicates that at least figures 1, 2 and 3 represent measured crystals with the relative prominence of faces in the drawings approximately corresponding to that of the actual crystals. It is therefore easy to assume that the crystal depicted in fig. 3 of CP41 (see fig. 1 above) is also tabular. However, as determined from the Miller indices given in the paper, along with the angles of inclination of the faces from the c-axis, this cannot be the case. Using the axial dimensions given by Palache and the Miller indices corresponding to the crystal illustrated in fig. 3 of his paper, the Macintosh version of the crystal- drawing program SHAPE (Dowty and Richards, 1993) was used to redraw the crystal. The sizes of the faces were adjusted to match Palache's fig. 3 when viewed directly down the c-axis (fig. 1 above). SHAPE was then simply used to rotate the crystal to be viewed away from the c-axis, whereupon its barrel-shaped morphology immediately became apparent (see fig. 2a). Such a morphology for graphite is very uncommon [compare, however, Kvasnitsa et al. (1988)]. As Palache mentioned that most of the crystals did not have well-developed faces on both the top and bottom halves, the crystal corresponding to Palache's fig. 3 might be only a fraction of that depicted in fig. 2a, as shown in fig. 2b. Unfortunately, attempts to locate this or any of the other studied graphite crystals at the Harvard Mineralogical Museum have failed. A batch of insoluble residues from Bauer has been preserved in a collection recently donated by John L. Baum (J. L. Baum, personal communication, 1992) to the U.S. National Museum of Natural History, but is currently unavailable for study (P. J. Dunn, personal communication, 1993).

.
Post-Publication Note:1-mm Graphite crystals from acid residues in the L.H. Bauer collection in the Smithsonian do show the barrel-shaped habit.


TWINNING


(c)
Fig. 3. (a) Graphite crystal from Sterling Hill (fig. 6 in CP41 recreated using SHAPE) with forms c{0001} and p{10-11}, showing a single twin lamella on {11-21}. The bottom of the crystal is a cleavage plane. (b) Side view of (a) showing that the twin lamella (shaded) is inclined by theta=20deg 36' from the adjacent, untwinned parts of the same crystal. (c) Graphite crystal from Bauer residues donated to the Smithsonian (National Museum of Natural History)

Palache sought crystals that were free from striations for goniometric measurement. Striations are commonly observed on the basal faces of graphite crystals and have long been recognized as due to mechanical twinning (Sjgren, 1884). These striations always are oriented diagonally to the hexagonal outline, i.e., along <1-100> directions, and can be induced by the application of only the slightest stress; thus, untwinned, unstriated crystals are rare. By observing an approximate 20deg angle between the basal pinacoids of a twin lamella and the adjacent, untwinned parts of the same crystal, Palache determined that the twin law is by reflection and composition on {11-21} planes (see fig. 3). Palache was apparently the first to identify the twin law, and such is the reason that a large number of subsequent authors have cited CP41. Palache also noted a twin lamella at an angle 16deg 43', corresponding most nearly to a {44-83} twin plane. Growth twins on this twin law as well as other twin laws are now also known (Laves and Baskin, 1956; Freise and Kelly, 1961; Shafranovskii, 1981, 1982, 1983; Jaszczak, 1991, 1992) from several localities.

CONCLUSION

Charles Palache's 1941 paper was not only an important contribution to the mineralogy of Sterling Hill, New Jersey, but was also a unique and important contribution to the descriptive mineralogy of graphite. The natural crystals described and drawn by Palache are a recognized standard for well-formed graphite crystals and are still considered to be some of highest quality crystals reported in the literature. Information regarding the existence or availability of Palache's graphite crystals or additional material such as that etched by Bauer would be greatly appreciated.

ACKNOWLEDGMENTS

I am most grateful to John L. Baum of the Franklin Mineral Museum for providing information and encouragement to write this article. I am indebted to Dr. Carl Francis for assistance in trying to locate the graphite crystals in the Harvard Mineralogical Museum collection. I am grateful to Sharon Cisneros for bringing the reference by Edwards (1976) to my attention.

REFERENCES

Austerman, S. B., Myron, S. M., and Wagner, J. W. (1967) Growth and characterization of graphite single crystals. Carbon 5, 549-557.

Dowty, E., and Richards, R. P. (1993) SHAPE, a computer program for drawing crystals. Macintosh Version 4.0.

Freise, E. J., and Kelly, A. (1961) Twinning in graphite. Proceedings of the Royal Society (London) A 264, 269- 276.

Frondel, C. (1955) Memorial of Lawson H. Bauer. American Mineralogist 40, 283-285.

Jaszczak, J. A. (1991) Graphite from Crestmore, California. Mineralogical Record 22, 427-431.

Jaszczak, J. A. (1992) Growth twinning in graphite from Crestmore and Jensen quarries, Riverside County, California. Rocks and Minerals 67, 114-115. (Abstract.)

Kolic, J. and Sanford, S. (1993) Recent mineral finds from the Sterling Mine, Ogdensburg, New Jersey. The Picking Table 34 (2), 12-21.

Kvasnitsa, V. N., Krochuk, V. M., Melnikov, V. S., and Yatsenko, V. G. (1988) [Crystal morphology of graphite from magmatic rocks from the Ukrainian Shield.] Mineralogicheskii Zhurnal 10(5), 68-76. (In Russian with English summary.)

Laves, F., and Baskin, Y. (1956) On the formation of the rhombohedral graphite modification. Zeitschrift fur Kristallographie 107, S.337-356.

Minkoff, I. (1979) Graphite crystallization. In, Preparation and Properties of Solid State Materials, vol. 4. Morphological Stability, Convection, Graphite, and Integrated Optics. Wilcox, W. R., editor. (Marcel Dekker, New York) 1-48.

Minkoff, I. (1983) The Physical Metallurgy of Cast Iron. (John Wiley and Sons, New York) p. 9.

Palache, C. (1941) Contributions to the mineralogy of Sterling Hill, New Jersey: Morphology of graphite, arsenopyrite, pyrite, and arsenic. American Mineralogist 26, 709-717.

Palache, C., Berman, H., and Frondel, C. (1944) The System of Mineralogy of James Dwight Dana and Edward Salisbury Dana, Yale University 1837-1892. Seventh edition, vol. 1. (John Wiley & Sons, New York) 152.

Shafranovskii, G. I. (1981) [New graphite twins.] Zapiski Vsesoyuznogo Mineralogicheskogo Obschestva 110, 716- 720. (In Russian.)

Shafranovskii, G. I. (1982) [Graphite twins and triads.] Mineralogicheskii Zhurnal 4(1), 74-81. (In Russian with English summary.)

Shafranovskii, G. I. (1983) [Classical and non-classical graphite twins.] Zapiski Vsesoyuznogo Mineralogicheskogo Obschestva 112, 577-581. (In Russian.)

Sjogren, H. (1884) Om grafitens kristallform och fysiska egenskaper. fversigt af Svenska Vetenskapsakademien Forhandlingar 44, 29-53.

Wilcox, W. R. editor (1979) Preparation and Properties of Solid State Materials, vol. 4. Morphological Stability, Convection, Graphite, and Integrated Optics. (Marcel Dekker, New York).

APPENDIX

Chronologic list of publications in which Palache's 1941 paper (American Mineralogist 26, 709-717) has een cited [not including this paper]. As this list is almost certainly incomplete, the author invites notification of additional publications that should be included.

1. Valter, A. A., Eremenko, G. K., Kvasnitsa, V. N., and Polkanov, Yu. A. (1992) Udarno- Metamorphogennure Mineralur Ugleroda [Shock- Metamorphic Minerals of Carbon.] (Naukova Dumka, Kiev) 172 pp. (In Russian.)

2. Jaszczak, J. A. (1992) Growth twinning in graphite from Crestmore and Jensen quarries, Riverside County, California. Rocks and Minerals 67, 114-115. (Abstract.)

3. Pengra, D. B., and Dash, J. G. (1992) Edge melting in low-coverage adsorbed films. Journal of Physics- Condensed Matter 4, 7317-7332.

4. Jaszczak, J. A. (1991) Graphite from Crestmore, California. Mineralogical Record 22, 427-432.

5. Kvasnitsa, V. N., Krochuk, V. M., Melnikov, V. S., and Yatsenko, V. G. (1988) [Crystal morphology of graphite from magmatic rocks from the Ukrainian Shield.] Mineralogicheskii Zhurnal 10(5), 68-76. (In Russian with English summary.)

6. Minkoff, I. (1983) The Physical Metallurgy of Cast Iron. (John Wiley and Sons, New York). Includes figure 5, but not figure 3, from Palache (1941) on page 9.

7. Shafranovskii, G. I. (1982) [Crystallomorphology of graphite from the Ilmen Mountains.] In, Mineralogicheskie Issledovaniya Endogennurkh Mestorozhdenii Urala. (Academiya Nauk SSSR- Uralskii Nauchnuri Tsentr) 44-53. (In Russian.)

8. Shafranovskii, G. I. (1982) [Graphite twins and triads.] Mineralogicheskii Zhurnal 4(1), 74-81. (In Russian with English summary.)

9. Shafranovskii, G. I. (1981) [New graphite twins.] Zapiski Vsesoyuznogo Mineralogicheskogo Obschestva 110, 716-720. (In Russian.)

10. Minkoff, I. (1979) Graphite crystallization. In Preparation and Properties of Solid State Materials, vol. 4. Morphological Stability, Convection, Graphite and Integrated Optics. Wilcox, W. R., editor. (Marcel Dekker, New York) 1-48. Includes figures 3 (also on the book cover) and 5 from Palache, 1941.

11. Munitz, A., and Minkoff, I. (1978) 45th International Foundry Congress Paper (Hungary). See Peiyue, Z., Rozeng, S., and Yanxiang, L. (1985) Effect of twin/tilt on the growth of graphite. In, The Physical Metallurgy of Cast Iron, Fredriksson, H. and Hillert, M., editors. MRS Symposium Proceedings, vol. 34. (North Holland, New York) 3-11.

12. Edwards, F. Z. (1976) The post Palache minerals. The Picking Table 17 (2), 6-10. It is quite evident that Palache's interest was primarily with the graphite crystals imbedded in the calcite. It is also probable that the specimens submitted by Dr. Bauer were all consumed by acid. At any rate, very few pieces of this occurrence may be found in collections today. p. 7. "It should also be mentioned that equally scarce and much unappreciated are the graphite crystals which so intrigued Dr. Palache." p. 8.

13. Akhmatov, Y. S., Bunin, K. P., and Taran, Y. N. (1975) [Mechanism of formation of graphite spherocrystals in Fe-Ce melt.] Dopovidi Akademii Nauk Ukrainskoi RSR Seriya A- Fiziko-Matematichni Ta Technichninauki (5), 453-455. (In Russian.)

14. Nagornyi, V. G., Nabatnikov, A. P., Frolov, V. I., Deev, A. N., and Sosedov, V. P. (1975) [Occurrence of a new crystalline form of carbon.] Zhurnal Fizicheskoi Khimii 49(4) 840-845. (In Russian.)

15. Akhmatov, Y. S., Taran, Y. N., Stepanchuk, A. N., Lisnyak, A. G., and Zaspenko, N. Y. (1974) Structure and mechanism of growth of graphite crystals with different genetic origins. Russian Metallurgy- USSR (4), 58-60.

16. Skinner, J., and Gane, N. (1973) The deformation and twinning of graphite crystals under a point load. Philosophical Magazine 28, 827-837.

17. Frondel, C. (1972) The Minerals of Franklin and Sterling Hill: A Check List. (Wiley-Interscience, New York) p. 58. Tiny but unusually perfect graphite crystals have been found in acid-insoluble residues of the marble-- see Palache (1941).

18. Double, D. D., and Hellawell, A. (1969) The structure of flake graphite in Ni-C eutectic alloy. Acta Metallurgica 17, 1071-1083.

19. Gmelins Handbuch der Anorganischen Chemie (1968) System-nummer 14. C- Kohlenstoff. Teil B, Lieferung 2. Das Element: Graphit. (Verlag Chemie, GMBH, Weinheim/Gergstr.) 409, 412. (In German.)

20. Austerman, S. B., Myron, S. M., and Wagner, J. W. (1967) Growth and characterization of graphite single crystals. Carbon 5, 549-557.

21. Baker, C., Gillin, L. M., and Kelly, A. (1966) Twinning in graphite. Second Conference on Industrial Carbon and Graphite. (Society of Chemical Industry, London) 132-138.

22. Amelinckx, S., Delavignette, P., and Heerschap, M. (1965) Dislocations and stacking faults in graphite. In, Chemistry and Physics of Carbon, Walker, P. L., Jr., editor. (Marcel Dekker, New York) 1-71.

23. Thomas, J. M. (1965) Microscopic studies of graphite oxidation. In, Chemistry and Physics of Carbon, Walker, P. L., Jr., editor. (Marcel Dekker, New York) 121-202.

24. Freise, E. J., and Kelly, A. (1961) Twinning in graphite. Proceedings of the Royal Society (London) A 264, 269-276.

25. Kennedy, A. J. (1960) Dislocations and twinning in graphite. Proceedings of the Physical Society (Great Britain) 75, 607-611.

26. Academiia Nauk SSSR. Institut Geologii Rudnykh Mestorozhdenii, Petrografii, Mineralogii i Geokhimii. (1960) Mineraly; Spravochnik, vol. 1. (Izd-vo Academii Nauk SSSR, Moscow) 69-75. (In Russian.)

27. Foster, L. M., Long, G., and Stumpf, H. C. (1958) Production of graphite single crystals by the thermal decomposition of aluminum carbide. American Mineralogist 43, 285-296.

28. Platt, J. R. (1957) Atomic arrangements and bonding across a twinning plane in graphite. Zeitschrift fr Kristallographie 109, S.226-230.

29. Palache, C., Berman, H., and Frondel, C. (1944) The System of Mineralogy of James Dwight Dana and Edward Salisbury Dana, Yale University 1837-1892. Seventh edition, vol. 1. (John Wiley and Sons, New York) 152. Includes figures 3 and 5 from Palache, 1941.


Back to MTU Physics Page
Back to Jaszczak's home page
Back to Jaszczak's graphite page