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Mineral. Deposita (Bed.) 3, 375--380 (1968)

The Cu--Se System

G. P. BERNARDINI and A. CATANI

Centro di Studio per la Geochimica e la Mineralogia del C. N. R., Istituto di Mineralogia dell' Universta di Firenze, Italy

Phase-relations in the Cu--Se system were determined by evacuated silica-tube experiments. The phase diagram up to 1100 ° C was obtained from the results of differential thermal analyses of pure compounds and of their mixtures. The phases in the system are: CurSe -- undergoes a polymorphic transformation at 150 ° C. The symmetry of the low temperature form is not yet known. The high form is cubic with a fluorite-type structure. Cu2-xSe -- cubic, with x variable in a very narrow range, at room temperature. CuaSe2 -- tetragonal, breaks down to Cu2-xSe and CuSe at 150 ° C. CuSe -- hexagonal below 60 ° C and, presumably, orthorhombic at higher temperature, melts incongruently at 387 ° C to Cug.-xSe and a Se-rich liquid. CuSe2 -- orthorhombic, melts in- congruently at 347 ° C to CuSe and a Se-rich liquid. The presence of an eutectie at 523 ° C was inferred from differential thermal heating and cooling curves.

Die Phasenbeziehungen im Cu-Se System wurden durch Versuche mit Hilfe evakuierter Quarzampullen bestimmt. Bis zu 1100 ° C wurden die Ergebnisse der Differential-Thermoanalyseverwendet. Die Phasen im System sind: Cu 2Se:

wandelt sich bei 150 ° C polymorph um. Die Symmetric der Tieftemperatur- form ist noch nicht bekannt, w~hrend die Hochtemperaturform kubisch ist (Flusspatstruktur). Cu2-xSe (kubisch) hat bei Raumtemperamr einen sehr kleinen x-Weft. CusSes (tetragonal) spaltet sich bei 150°C zu Cue-xSe und CuSe. CuSe (hexagonal) ist unterhalb 60 ° C vermutlieh rhombisch und bei h6herer Temperatur (387°C) zersetzt es sich inkongruent zu Cu~-xSe und einer Se-reichen Schmelze. CuSe2 (rhombisch) zersetzt sich bei 347°C inkon- gruent zu CuSe und einer Se-reichen Schmelze. Die Anwesenheit eines Eutek- tikum bei 523 ° C wird aufgrund yon DTA-Analysen angenommen.

Many authors (CoLEmAN and DELAVAUX 1957, HAWLEY and NICHOL 1959, MclNTmE 1963, LOFTus--HILL and SOLOMON 1967) have drawn attention to the S: Se ratio as a promising indicator of sulfide ore genesis. In spite of this, few ternary systems involving Se have been studied. As a part of an investigation of the stability relations in the ternary system Cu-S--Se, the binary Cu--Se was investigated. The phase relations in the Cu--Se system at room temperature were studied by BORCHERT and PATZAK (1955), while GATTOW and SCHNEI- DeR (1956) studied some thermodynamic properties of these phases. HANSEN and AN-

25*

DERKO (•958) and E* LIOTT (1965) reviewed the phase relations in the range of composition between 0 and 45 X wt. per cent Se at tempera- tures above 900 ° C, as well as some properties of the intermediate phases. HEYDING (1966) ob- taine da phase diagram up to 880 ° C and esti- mated the enthalpies of transformation of some compounds, while DIES (1967) reviewed some physical properties of the compounds with very low Se contents. The results of the in- vestigations reviewed by DIEs (1967) and those obtained in the present research are incorporated in Fig. 1. Experiments were carried out using silica- glass capsules as sample containers for the

376

G.P.

BERNARDINIand A. Ci~riNI

1200~

1083~/'////////~1 "/1063°/'//////S///y/4~x~/

1000 "3(/~

2 liquids

o

~6oo

E

400

200

25

Cu

2

150o±5°

5

2~0

Cu2Se/'

n,

tl

711

|!

II

II

l

9

150o*_5o

14

10 1

11

60°±5°

~

12

13

Cu3Se2

CuSe 60

Weight per cent Se

5230±5°

3870±5°

3470±5°

16

2270±5°

17

CuSe,

8b

I00

 

Se

Fig. 1. Phase relations in the Cu--Se system above 25°C Phases present in addition to vapor in the numbered fields are*:

(1) liquid+ ~ Cu2Se; (2) Cu+ ~ Cu2Se; (3) Cu+ Hquid; (4) liquid+Cu~-xSe; (5) Cu+= Cue Se; (6) c~Cu2Se + Cu2-xSe; (7) Cu2-xSe + liquid; (8) Cu2-xSe + liquid; (9) Cu2-xSe + CuSe h.t.; (10) Cu~-xSe+CusSe2; (11)CusSe2+CuSe h.t.; (12) Cu3Se2+CuSe 1.t.; (13) CuSe 1.t.+CuSe2; (14) CuSe h.t.+CuSe2; (15) CuSe h.t.+liquid; (16) CuSe2+liquid; (17) CuSe2 + Se

* The hatched region in the diagram is from DIES- (1967); h. t. = high temperature; 1.t. = low temperature.

synthesis of compounds as well as for their differential thermal analysis. The method employed, described elsewhere (BERNARDINI

1966), iS similar to

the one developed by

KULLERIJD and YUND (1962). The diagram of Fig. 1 is based on the results of differential

thermal analysis (D. T.A.) of pure

compounds and of their mixtures up to a maximum temperature of 1100 ° C, as well as on the results of a few quenching experiments. As all experiments were carried out in rigid capsules, vapor is a phase in all assemblages. The results of all differential thermal runs are given in the Table 1.

synthetic

t AU temperatures in D.T.A. given with -4-5° C accuracy.

experiments are

Phases in the System

Cu2Se. According to I~ALACI-IE,BERMAN and FRONDEL (1944), RAMDOHR (1960) and STRUNZ (1966), the natural equivalent is the mineral berzelianite, while this name is given by EARLEY (1950), BORCHERT and PAWZAK (1955) and BERRY and THOMPSON (1962) to the Cu2-xSe compound. The symmetry of Cu2Se below 150 ° C (~ form) is not known according to HBYDING (1966), while BORCHERT (1945) suggested Cu2 Se to be tetragonal and ELLIOTT (1965) body centered cubic. Above 150 ° C (~ form), Cu2Se is cubic with a fluoritetype structure (RALI'HS 1936, BORCHERT 1945). D.T.A. experiments show no other thermal effect below 1100 ° C except the one at 150°C due to high-low inversion. The temperature

The Cu--Se System

377

Table. Differential thermal analysisofpure syntheticcompoundsand of fheir mixtures

Composition

Thermal effect on heating*

Wt% Se

Phases

T (o C)

Interpretation

100

Se

227

melting Se

96.0

Se

q- CuSe2

227

melting Se

 

347

incongruent melting CuSe2

387

incongruent melting CuSe

523

eutectic melting

88.1

Se -t-CuSe2

227

melting Se

 

347

incongruent melting CuSe2

387

incongruent melting CuSe

523

eutectic melting

77.6

Se -}-CuSe2

228

melting Se

 

342

incongruent melting CuSe2

387

incongruent melting CuSe

523

eutectic melting

73.7

Se

q- CuSe2

230

melting Se

 

342

incongruent melting CuSe2

387

incongruent melting CuSe

520

eutectic melting

71.3

CuSe2

347

incongruent melting CuSe2

 

390

incongruent melting CuSe

523

eutectic melting

69.2

CuSe2 -t-CuSe

345

incongruent melting CuSe2

 

385

incongruent melting CuSe

522

eutectic melting

66.6

CuSe~ -t-CuSe

342

incongruent melting CuSe~

 

392

incongruent melting CuSe

523

eutectic melting

63.2

CuSez q-CuSe

340

incongruent melting CuSe2

 

385

incongruent melting CuSe

523

eutectic melting

61.8"*

CuSe~ q- CuSe

57

1.~h. CuSe inversion

 

347

incongruent melting CuSez

387

incongruent melting CuSe

59.8

CuSe2q- CuSe

342

incongruent melting CuSe2

 

387

incongruent melting CuSe

525

eutecfic melting

58.8

CuSe2 q- CuSe

58

l.~h. CuSe inversion

 

342

incongruent melting CuSe2

385

incongruent melting CuSe

525

eutectic melting

* Thermal effects on cooling are not reported since the diagram of Fig. 1 is constructed on data of heating curves. Cooling curves indicate lower tempera- tures of transition owing to supercooling effects.

378

G.P. BERNARDINIandA. CATANI

Table (continued)

 

Composition

 

Thermal effect on heating*

Wt% Se

Phases

T

(o C)

Interpretation

55.4

CuSe

390

incongruent melting CuSe

 

522

eutectic melting

55.4

CuSe

392

incongruent melting CuSe

 

528

eutectic melting

55.4

CuSe

60

1.-*h. CuSe inversion

 

390

incongruent melting CuSe

525

eutectic melting

55.4

CuSe

57

1.-~h. CuSe inversion

53.4

CuSe + Cu~-xSe

65

1.~h. CuSe inversion

 

390

incongruent melting CuSe

525

eutectic melting

50.0

CuSe + Cu2-xSe

65

1.--~h. CuSe inversion

 

387

incongruent melting CuSe

523

eutectic melting

46.3**

CuSe +

Cu2-xSe

150

Cua Se2 disappears

 

385

incongruent melting CuSe

525

eutectic melting

45.3

Cu3 Sez (with traces of CuSe and Cu2-xSe)

152

CusSe2 disappears

 

387

incongruent melting CuSe

525

eutectic melting

45.3

CurSes (with traces of CuSe and Cu2-xSe)

150

CusSe~ disappears

 

380

incongruent melting CuSe

525

eutectic melting

45.3

CusSes (with traces of CuSe and Cu~-xSe)

145

CuBSe2 disappears

 

382

incongruent melting CuSe

527

eutectic melting

45.3

Cu3 Sez (with traces of CuSe and Cu2-xSe)

145

Cua Se2 disappears

 

387

incongruent melting CuSe

525

eutectic melting

45.3

Cur Se2 (with traces of CuSe and Cu2-xSe)

148

Cua Se~ disappears

 

387

incongruent melting CuSe

523

eutectic melting

45.3**

Cut.

s0 Se +

CuSe

385

incongruent melting CuSe

 

520

eutectic melting

45.3**

Cul. s0 Se +

CuSe

385

incongruent melting CuSe

 

525

eutectic melting

** D. T. A. runs on preheated materials.

The Cu--Se System

379

Table (continued)

 

Composition

Thermal effect on heating*

 

Wt% Se

Phases

T

(o C)

Interpretation

44.2**

Cul.s0Se + CuSe

150

Cus See disappears

 
 

385

incongruent melting CnSe

522

eutectic melting

 

41.8"*

Cui.80Se +CuSe

155

Cua See disappears

40.9

Cui.s0Se

 

40.4

Cul. s5 Se

39.9

Cul.s5 Se +

Cue Se

100

c¢-+}Cu2 Se inversion

 

39.8

Cul.s5

Se +

Cue Se

97

c~+~ Cue Se mvermon

39.5

Cut.s5 Se +

Cue Se

110

~-+~ Cue Se Inversion

38.8

Cul.s5

Se +

Cu2 Se

130

~

Cu28e reversion

38.3

Cui.ssSe +Cu

150

~+~ CueSe inversion

38.3

Cu~Se

135

c~-~ Cue Se inversion

38.3

Cu~Se

145

c~-+~CueSe inversion

38.3

Cu2 Se

145

:¢-+~Cu2 Se

reversion

38.3

Cu2 Se

140

~--~ Cu2 Se

Inversion

38.3

Cue Se

145

c~+~ Cue Se inversion

 

28.7

Cu2 Se +

Cu

150

c¢-~

Cue Se inversion

 

1060

eutectic melting

19.3

Cue Se +

Cu

150

~--*} CurSe inversion

 

1063

eutectic melting

9.6

CueSe +Cu

152

e-~} Cue Se inversion

 

1063

eutectic melting

0.0

Cu

1075

Cu melting

of this inversion is lowered by the addition of Se (as noticed by RALI~I-ISin his x-ray analysis and by HERDINGin his cooling curves). Cu2-xSe, with 0.15 ~< x ~< 0.20, according to BORCHERT and PATZAK (1955), is cubic with the structure of the ~ Cu2Se phase. The unit cell parameter varies linearly from 5.745 _h for Cul.85Se to 5.730 A for Cul.s0Se. D.T.A. experiments of these two compounds show no thermal effects whatsoever. The limits of solid solution at room and higher temperatures are under investigation in order to control the trend of the Se-rich boundary suggested by HERDING (1966). Cu3 Se2 -- which has a natural equivalent in the mineral umangite (EARLEY1950) -- has a very low reaction rate. Synthesis at different tem- peratures below 150 ° C always gives mixtures

of CuaSe2 with Cu2-xSe and CuSe. In experi- ments performed at room temperature, the amount of CuaSe~ increases with time at the expense of the other two metastable phases. D.T.A. experiments show that at 150°C Cu3Sez breaks down to Cu2-xSe and CuSe (in accordance with the high-temperature x-ray work of RALI'HSand HEYDING). The presence of four phases: Cu2-xSe, CurSe2, CuSe, and the vapor phase, at this temperature fulflles the requirements of invariancy in a two-component system. CuSe -- which has a natural equivalent in the mineral klockmannite (EAitLEY 1949) -- is hexagonal with a superstructure (P63/m), due to the presence of twinning (DONNA* 1956, TAYLORand UND~I~WOOD1960, LII'I'MAN1962), derived from the structure of CuS (P63/mmc).

380

G.P. BERNARDINI and A. CATANI,The Cu--Se System

D.T.A. experiments show a thermal effect at 60°C that indicates a low-high inversion probably caused by a readjustment of the superstructure. CuSe melts incongruently at 387 ° C to Cu2-xSe and a Se-rich liquid. CuSe2 is an orthorhombic phase synthesized for the first time by BORCHERT and PATZAK (1955). GATTOW (1965) has given the cell and atomic parameters for a marcasite-type struc- ture. This compound, easily synthesized even at low temperature in a short period of time, melts incongruently at 345 ° C to CuSe and a Se-rich liquid. From quenching experiments the presence of an eutectic at about 45 wt. per cent Se was inferred. The field of two liquids plus vapor, which exists above 523 ° C, extends from this point to a composition with more than 97% Se. Cu2-xSe plus liquid and vapor phases are present on the other side of the eutectic com- position above 523 ° C. The determination of the boundaries of these two fields and of possible limited solid solution around the composition of the stable phases at different temperatures is in progress.

References

BERNARDINI, G. P.: Studio diffrattometrico e pirosintetico della serie CuS--CuSe. Periodico Mineral. (Rome) 35, 898--923 (1966).

BERRY,L. G., and R. M. THOM,SON:X-ray powder data for ore minerals: the Peacock Atlas. Geol. Soc. Am., Mere. 85, 40 (1962). BORCHERT,W.: Gitterumwandlungen im System Cu2-xSe. Z. Krist. Mineral. Petrog. 106, 5--24

(1945).

--, u. I. PATZAK: Reaktionen im festen Zustand yon Kupfer und Silber mit Selen. Heidelberger Beitr. Mineral. und Petrog. 4, 43 a, a.A.2(1955). COLEMAN,R. G., and M. DELEVAUX:Occurrence of selenium in sulfides from some sedimentary rocks of the Western United States. Econ. Geol. 52, 499--527 (1957).

Kupferlegierungen in der

DIES, K. : Kupfer und

Technik. Berlin-Heidelberg-New York: Sprin- ger 1967. DONNAY,G. : Klockmannite. Carnegie Inst. Wash., Year Book 55, 205 (1956). EARLEY, J. W. : Studies of natural and artificial selenides. I: !dockmannite CuSe. Am. Miner- alogist 34, 435 dA.0(19497.

-- Description and synthesis of the selenide min- erals. Am. Mineralogist 35, 337--364 (1950).

ELLIOTT, R. P. : Constitution of bynary alloys, 1st supplement. New York: McGraw-Hill 1965.

GATTOW, G.: Beitrag zur Kristallchemie des Systems Kupfer-Selen. Naturwissenschaften 10, 258 (1965).

--, u. A. SCHNEIDER:Die Bildungsenthalpien im System Kupfer-Selen. Z. Anorg. Atlgem. Chem. 286, 296--306 (1956).

HANSEN, M., and K. ANDERKO: Constitution of binary alloys. New York: McGraw-Hill 1958.

HAWLEY,J. E., and I. NICHOL: Selenium in some Canadian sulfides. Econ. Geol. 54, 608--628

(1959).

The

Can. J. Chem. 44, 1233--1236 (1966).

HEYmNO, R.

D.:

copper-selenium

system.

KULLERUD,G., and R. A. YUND: The Ni--S system

and

(1962).

related

minerals.

J:

Petrol.

3,

126-175

LIPrmtNN, F. : Zur Deutung der Uberstruktur des Klockmannits, CuSe. Neues Jahrb. Mineral., Monatsh. 99--105 (1962).

LOrTus-HILL, G., and M. SOLmaON:Cobalt, nickel and selenium in sulfides as indicators of ore genesis. Mineral. Deposita (Berl.) 2, 228--242

(1967).

MCINTIRE, W.

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Cosmochim. Acta 27,

1209--1264 (1963). PALACHE, C., H. BERMAN,and C. FRONDEL: The system of mineralogy. Vol. I. New York: John Wiley 1944.

Hochtemperatur-

RALPHS, P.: Uber die kubischen

L.: Trace element partition coeffi-

to

geology.

Geochim.

modifikationen der Sulfide, Selenide und Tellu- ride des Ag und einwertigen Cu. Z. Physik.

Chem. B 31, 157--194 (1936).

RAMDOHR, P.: Die Erzmineralien und ihre Ver-

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Leipzig:

wachsungen.

Berlin:

Akademie-Verlag

Tabellen.

STRUNZ, H.:

Akademische VerlagsgeseUschaft 1966. TAYLOR,C. A., and F. A. UNDERWOOD:A twinning interpretation of superlattice reflexions in x-ray hotographs of synthetic klockmannite, CuSe. eta Cryst. 13, 361--362 (1960).

Received July 11, 1968

Dr. G. P. BERNARDINIand Dr. A. CATANI Istituto di Mineralogia, Petrografia e Geochimica dell'Universit~ degll Studi di Firenze, Via Lamar- mora 4, 1-50121 Firenze, Italy

Mineralogische