manganese s p i n e l is achieved a t llOOC.

(2) Under mildly reducing conditions in which magnetite a n d manganosite a r e thermodynamically s t a b l e p h a s e s , reaction between iron and manganese r e s u l t s in t h e formation of e x t e n s i v e manganese-bearing wustite (manganowustite) a t temperatures a s low a s 800C. T h e s e d a t a s u g g e s t that under normal mangnetizing roasting conditions significant quantities of manganowustite a n d , by inference, s u b s t a n t i a l amounts of iron-manganese s p i n e l must form. T h i s c a n in part explain t h e erratic and unpredictable behavior of some manganiferous iron o r e s in magnetizing roasting. (3) R e a c t i o n s between iron and s i l i c a a r e significant under mildly reducing conditions, and magnetite will react with s i l i c a t o form s u b s t a n t i a l quantities of fayalite a t 900C. T h e s e reactions occur a t lower temperatures under moderately reducing conditions in which w u s t i t e i s t h e s t a b l e iron o x i d e phase. (4) R e a c t i o n s between pure MnO a n d s i l i c a a r e not nearly a s extensive, nor d o they t a k e p l a c e a t a s low temperatures a s t h e iron-silica reactions. T h e extens i v e reaction rims formed o n s i l i c a gangue during reduction of natural o r e s a r e the combined effects of iron and manganese reacting with s i l i c a . (5) During R-N reduction an e x t e n s i v e manganow u s t i t e p h a s e will form and t h e final metallization s t a g e for portions of t h e ore will involve exsolution of metallic iron from a n iron-rich manganosite. T h i s type of reaction would b e expected to be slower than direct reduction of pure w u s t i t e and may, in part, explain incomplete or e x c e s s i v e l y slow metallization in s o m e ores.

Minnesota, and t h e Economic Development Administration, U.S. Department of Commerce, for sponsoring t h i s investigation. They a r e a l s o indebted t o t h e Graduate School of the University of Minnesota for a grant covering t h e purchase of t h e high-temperature x-ray diffraction equipment.

REFERENCES
'c.K.
L

Leith: T h e Geology of t h e Cuyuna Iron Range, Minnesota. Econ. Geology, 1907, vol. 2, pp. 145-152.
~ . Adams: T h e Iron Formation of t h e Cuyuna R a n g e , ~ . Minnesota, Econ. Geology, 1910, vol. 5. pp. 729-740.

3 ~ Zapffe: Manganiferous Iron Ores of Cuyuna District, . Minnesota, AIME Transactions, 1925, vol. 71. pp. 372-385.
4 ~ . Grout a n d J . F . Wolff, Sr.: T h e Geology of t h e Cuyuna ~ .

District, Minnesota, Minnesota Geol. Survey Bull. 3 6 , 1955.

'R.G.

Schmidt: Geology and Ore D e p o s i t s of t h e Cuyuna North Range, Minnesota, Geol. Survey P r o f e s s i o n a l P a p e r 407, 1963.

6 ~ White: T h e P h y s i c a l Chemistry of Open-Hearth Slags, . l o u r n a l Zmn & S t e e l I n s t i t u t e (London), 1943, vol. 148, no. 11, pp. 579-698.

7 ~ . McMurdie, B.M. Sullivan, and F.A. Mauer: High-tempera~ . ture X-ray Study of t h e System Fe304-Mn304, J o u r n a l of R e
s e a r c h , National Bureau of Standards, R e s e a r c h P a p e r 2111. 1950, vol. 45. pp. 35-41.

'R.

Hay, D.D. Howat, a n d J. White: Slag Systems, Journal West S c o t l a n d Iron a n d S t e e l Institute. 1934, vol. 41, pp. 97-103.

'w.c.
''5.

Allen a n d R.B. Snow: T h e Orthosilicate-Iron Oxide Portion of t h e System CaO-'FeO1-SO2, Journal American Ceramic Society, 1955, vol. 38, pp. 264-280. White, D.D. Howat, and R. Hay: T h e Binary System Mn0-SiO2, Journal Royal T e c h n i c a l C o l l e g e (Glasgow), 1934. vol. 3, pp. 231, 240.

"w.M.

D r e s s e l and H. Kenworthy: T h e n n s l Behavior of Mangen e s e Minerals i n Controlled Atmospheres, U.S. Bureau of Mines Report of I n v e s t i g a t i o n s 5761, 1961.

ACKNOWLEDGMENTS
T h e authors a r e grateful t o t h e Iron Range Res o u r c e s and Rehabilitation commission, t h e State of

1 2 ~ Muan and S. Somiya: T h e System Iron Oxide-Manganese . Oxide i n Air, American Journal o f Science, 1962, vol. 260. pp. 230-240. 1 3 ~ . Morris and A. Muan: P h a s e Equilibria i n t h e System ~ . MnO-Mn203-Si02, Journal of Metals, 1966, vol. 18, no. 8, pp. 957-960.

TECHNICAL NOTE

HYDROGENATED COAL BITUMEN--A NEW MATERIAL FOR HIGHWAY CllNSTRUCTlON

by H. F. Silver

lthough t h e literature indicated t h a t a hydrogenated coal bitumen might b e u s e d a s a s u b s t i t u t e for petroleum a s p h a l t and road tar, no work could b e found i n which t h e material w a s actually u s e d or

evaluated a s a road binder.' Therefore, a study w a s initiated t o investigate the production and properties of a road binder made by hydrogenating coal in t h e presence of a solvent a t elevated temperatures and pressures.

H. F. SILVER is A s s o c i a t e Professor of Chemical Engineering and Chemical Engineer, Natural Resources Research Institute, University of Wyoming, Laramie, Wyo. TN 67F300. Manuscript, May 22, 1967. T h i s paper w a s presented a t the SME F a l l Meeting-Rocky Mountain Minera l s Conference, L a s Vegas, Nev., September 6-8, 1967.

HY DROGENATlON PROCEDURE
Four different s a m p l e s of sub-bituminous Wyoming c o a l s a n d three s a m p l e s of c o a l s from other s t a t e s , ranking from lignite t o a low-volatile bituminous coal,
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were investigated. Solvents studied have ranged from hexane t o lubricating oil fractions from petroleum s t o c k s and from benzene t o high-temperature carbonization c o a l tar fractions of varying boiling ranges. Descriptions of the properties of the c o a l s and solvents, a s well a s the equipment used, h a v e been reported.'-" For e a c h c o a l hydrogenation run, approximately 1 0 0 gm of ball-milled c o a l and 400 gm of solvent were first charged t o an Aminco rocking reactor. Once the desired initial hydrogen pressure had been obtained, the reaction mix w a s heated t o temperatures ranging from 675" t o 82SF. At the end of a predetermined length of time varying from 1/2 hr t o 8 hr, t h e reaction product w a s cooled and removed from the reactor for a n a l y s i s and evaluation.

BITUMEN YIELDS
Hydrogenated c o a l bitumen yields ranged from essentially zero t o nearly 100 weight percent of the moisture-ash-free (hlAF) c o a l charged t o the reactor. Bitumen yields of over 8 0 weight percent of the MAF coal were common from runs in which low rank c o a l s were hydrogenated in the presence of low-boilingrange c o a l t a r fractions. T h e product from runs made with l e s s efficient solvents, s u c h a s the paraffins, and from runs made with higher rank c o a l s included large amounts of a brittle, solid residue which w a s unsuitable for highway c o n s t r ~ c t i o n . ' ~ ~

tory have had VTS's ranging from 4 . 1 to 5.6, while road tars h a v e had slightly higher VTS's, ranging from 5.3 t o 6.9. T h e e f f e c t s of aging on a bitumen h a v e b e e n correlated by a parameter called the retained viscosity (RV). T h i s parameter i s the ratio of the viscosity of a bitumen sample aged in a 1/8-in.-thick layer a t 140F for 72 hr t o the viscosity of a n unaged sample. A low RV value h a s been assumed t o indicate that the quality of the bitumen will not change significantly during the life of the road. T h e RV's of a s phalts measured in this laboratory h a v e ranged from 1 . 1 t o 2 . 2 , while the RV's of road tars have ranged from 5.3 to 8.0. T h e highest quality hydrogenated c o a l bitumens have been produced u s i n g low rank c o a l s and c o a l tar fractions a s solvents. T h e VTS's of bitumens produced from t h e s e materials h a v e averaged approximately 4.8. T h e RV's of t h e s e products h a v e shown considerable variation, ranging from slightly l e s s than 2 . 0 t o over 5.0.

CONCLUSIONS
T h e work completed thus far indicates that hydrogenated c o a l bitumen c a n b e produced in good yield from coal. T h e actual yields obtained, a s well a s t h e properties of t h e bitumen, depend not only on t h e reaction conditions used, but a l s o on the c o a l and the solvent used a s raw materials. Low rank c o a l s similar t o t h o s e found in Wyoming appear t o be the most reactive, a n d s o l v e n t s somewhat similar to t h o s e that would b e produced in t h i s c o a l hydrogenation process appear t o be effective. Laboratory evaluations indic a t e that a hydrogenated c o a l bitumen which h a s properties similar to t h o s e of a s p h a l t s and road tars may be produced. F i e l d t e s t s a r e warranted t o establish more completely t h e suitability of hydrogenated c o a l bitumen a s a road binder.

BITUMEN EVALUATION
Of the a s p h a l t and road-tar evaluation procedures currently being used, t h o s e based on measuring physical properties of t h e bitumens appeared to be most relevant. Therefore, several physical t e s t s , described in either the asphalt or c o a l tar literature, were applied t o s a m p l e s of a l l three types of bitumens." Preliminary work indicated that both road t a r s and hydrogenated c o a l bitumens had adhesive qualities in t h e presence of water that were superior t o t h o s e of asphalts.3 However, t h e consistency of asphalt appeared t o be l e s s affected by temperature than t h e consistency of road tars. Furthermore, there appeared t o be wide variations in the effect of aging on t h e consistency of both a s p h a l t s a n d road tars. Therefore, efforts were directed toward measuring the effects of temperature and of simulated aging on t h e consistency of t h e s e three bitumen products. T h e s e qualities h a v e been measured by means of a Canon Instrument Co. c o n e and plate viscometer. Temperature effects h a v e been correlated using a parameter c a l l e d t h e viscosity-temperature-susceptibility (VTS). T h i s parameter i s e s s e n t i a l l y a measure of t h e s l o p e of a temperature-viscosity curve. T h e consistency of bitumens with low VTS's changes relatively l i t t l e in the range of temperatures experienced by a road. Asphalts evaluated i n t h i s labora218 - J U N E 1968

ACKNOWLEDGMENTS
T h e a s s i s t a n c e of Mr. J. Calkins, Mr. J. Angelovich, and Mr. S. Jain, graduate a s s i s t a n t s , and Mr. B. Davis and Mr. H. Lorson, analytical chemists, i s gratefully acknowledged. Samples of c o a l tar c u t s donated by t h e U.S. Steel Corp., and s a m p l e s of Knife River lignite donated by the Knife River C o a l Mining Co., Glenrock c o a l donated by the P a c i f i c Power and Light Co., Wyodak c o a l donated by the Wyodak Resources Development Corp., Elk01 c o a l donated by t h e Kemmerer Coal Co., Hanna c o a l donated by t h e Rosebud C o a l S a l e s Co., and Buckeye c o a l donated by t h e Pocahontas F u e l Co., a division of T h e Consolidation Coal Co., a r e a l s o appreciated. T h i s work h a s been supported by a research contract from t h e Wyoming S t a t e Highway Department a n d the U.S. Bureau of P u b l i c Roads. T h e opinions, findings, and conclusions expressed in t h i s paper a r e t h o s e of t h e Natural Resources Research InstiTRANSACTIONS

tute and a r e not necessarily t h o s e of t h e Wyoming State Highway Department or t h e U.S. Bureau of P u b l i c Roads.

3 ~ . Silver, B.E. D a v i s , and W.E. Duncan: Coal Hydrogenation ~ . Study - Final Report t o t h e Wyoming Highway Department. Natural Resources R e s e a r c h Institute, University of Wyoming, Laramie, Wyo., J u n e , 1965. 4 ~ . Calkins end H.F. Silver: A Study of t h e Hydrogenation of a ~ . Wyoming Coal to Produce a Bltuminoua Cement for R o a d Construction, Preprint Zld, 62nd National Meeting, A.1.Ch.E.. Salt Lake C i t y , U t a h , May 21-24, 1967.

REFERENCES
'H.F.
Silver: Bituminous Cement from Coal Hydrogenation, Znformation Circular No. 39, Natural Resources Research Institute, University of Wyoming, L a r a m i e , Wyo., October, 1965.
Study Final Report to t h e Wyoming H i g h w a y Department. Natural Resources R e s e a r c h Institute. University of Wyoming. Laramie, Wyo., September, 1966.

2 ~ . ~ . . S i l v e ro a l Hydrogenation C:

's.c.

Jain: A Study of the Liquid Phase Hydrogenation of Coals. M a s t e r ' s Thesis in Chemical Engineering, University of
Wyoming, March, 1967.

STATISTICS OF RANDOM FRACTURE

by

L. G. Austin

and

R. R. Klimpel

T h i s a r t i c l e demonstrates that the Gilvarry a n d Klimpel-Austin equations for t h e random fracture of s o l i d s a r e incorrect by deriving intuitively correct expressions for s i m p l e c a s e s a n d showing that the foregoing equations d o n o t reduce to right answers. t is t h e purpose of t h i s a r t i c l e t o point out serious errors in some e x i s t i n g treatments of t h e random fracture of s o l i d s . Gilvarry gives the equation

'

and r v is t h e number of fracture planes originating from flaws within t h e particle volume. T h i s equation is a l s o incorrect. T h e failures of t h e s e equations will b e demonstrated by deriving intuitively correct e x p r e s s i o n s for simple c a s e s a n d showing that t h e E q s . 1 and 2 do not reduce t o the correct answer. In t h i s process, the f l a w s in s t a t i s t i c a l reasoning inherent in the derivations of Eqs. 1 and 2 become apparent.

B (y,x)

1 - e x p [ - (y/k) - (y/j)

- ( ~ / i I) ~ [11

THE KLIMPEL-AUSTIN EQUATION

Eq. 2 w a s derived by considering a s e t number of fracture p l a n e s occurring spatially a t random within a given particle. T h i s c a s e will b e treated here in i t s simplest form: a line with 1, 2, 3, etc., fractures occurring a t random. T h i s is illustrated in Fig. 1, with the original length of t h e l i n e a s Vo. T h e breakage of a long, thin, brittle fiber is a corresponding physical c a s e , with t h e volume of a fragment proportional t o i t s length. Assuming independence of t h e occurrence of the fractures, t h e probability of any o n e fracture occurring in length dV is dV/V0. T h e probability of the first fracture occurring a t a length V t o V + dV is dV/Vo. For t h e c a s e of only one fracture per particle, formation of a number-size distribution of t h e left-

where B ( y , x ) i s t h e cumulative fraction by weight of particles which fall below s i z e y when particles of s i z e x a r e broken. T h e c o n s t a n t s i, j, k contain s h a p e factors and d e n s i t i e s of flaws leading t o propagating fracture surfaces. T h e authors b e l i e v e t h i s equation t o b e incorrect. Klimpel and ust tin' give

where r~ is t h e number of fracture planes originating from e d g e flaws (per L where L is t h e e d g e length of the original particle), rs i s t h e number of fracture p l a n e s originating from flaws on t h e particle surface (per S where S is the s u r f a c e of t h e original particle)
L. G. AUSTIN, Member AIME, i s Professor of Chemical Engineering, Department of Chemical Engineering, North Carolina State University, Raleigh, N . C . , and R . R. KLIMPEL, Member AIME, i s Operations Research Analyst, Dow Chemical Co., Midland. Mich. TP 67B210. Manuscript, March 1, 1967. D i s c u s s i o n of this paper, submitted in duplicate prior to September 15, 1968, will appear in SME Transactions, December 1968, and AIME Transactions, 1968, vol. 241.

Fig. 1

- Random fracture occurring along a line representing length or volume.

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