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Accepted Manuscript

A morphological study of the sulfurisation of digenite to covellite using reflected


polarised light microscopy

Heidi Rask Møller Frøkiær, Terence E. Warner

PII: S1293-2558(17)30293-5
DOI: 10.1016/j.solidstatesciences.2017.06.005
Reference: SSSCIE 5511

To appear in: Solid State Sciences

Received Date: 7 March 2017

Accepted Date: 11 June 2017

Please cite this article as: H.R. Møller Frøkiær, T.E. Warner, A morphological study of the sulfurisation
of digenite to covellite using reflected polarised light microscopy, Solid State Sciences (2017), doi:
10.1016/j.solidstatesciences.2017.06.005.

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ACCEPTED MANUSCRIPT

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A morphological study of the sulfurisation of digenite to covellite using
reflected polarised light microscopy

Heidi Rask Møller Frøkiæra and Terence E. Warnerb,*


a
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55,
5230 Odense M, Denmark
b
Department of Chemical Engineering, Biotechnology and Environmental Technology, University of
Southern Denmark, Campusvej 55, 5230 Odense M, Denmark

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* Corresponding author
E-mail address: tew@kbm.sdu.dk (Terence E. Warner)

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ABSTRACT

A series of copper rods were reacted with sulfur vapour in evacuated glass ampoules at ∼445°C.

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Product materials were characterised by powder X-ray diffraction and reflected polarised light
microscopy. Copper sulfurised rapidly to digenite, γ-Cu2-xS, under these conditions, whereas the
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subsequent sulfurisation to covellite, CuS, was notably slower, yielding texturally distinguishable
inner (secondary) and outer (primary) CuS regions. A two-stage partial sulfurisation of γ-Cu1.8S
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resulted in the external growth of two successive layers of primary CuS, which demonstrates
decisively that covellite − besides being a p-type metal − is ionically conducting at 445°C, although
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considerably less so than digenite. We infer that the growth of platy covellite crystals and their
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radial alignment in the primary CuS layer are a consequence of copper ion mobility being
restricted to the basal plane of the covellite structure. Sulfurising a coil of copper wire at ∼445°C is
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an effective method for synthesising covellite.


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Highlights:
• CuS is ionically conducting at 445 °C although considerably less so than γ-Cu2-xS
• Alignment of CuS crystals is attributed to Cu+ ionic conduction in CuS basal plane
• The outer layer of CuS retards further sulfurisation of the underlying γ-Cu2-xS
• Reacting a coil of Cu wire with sulfur is an efficient method for synthesising CuS

Keywords:
A. Chalcogenides
B. Phase transitions
D. Diffusion
D. Ionic Conductivity
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1. Introduction

There are thirteen crystalline binary phases in the Cu−S system at ambient pressure,

although some of them, such as spionkopite, Cu1.4S, and yarrowite, Cu9S8, are considered to be

metastable [1]. Collectively they display a range of important electrical properties: Chalcocite,

α-Cu2S, is a direct bandgap p-type semiconductor that was used in the first efficient thin film solar

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cell [2]; digenite, γ-Cu2-xS, is a mixed (ionic/electronic) conductor [3] that also functions as a

cathode material for lithium-ion batteries (2Li+ + Cu2S + 2e− ⇌ Li2S + 2Cu) [4]; whilst covellite, CuS,

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was the first stoichiometric compound to display superconductivity [5]. Beside their relevance to

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the electronics industry, these charge and mass transport phenomena play a fundamental role in

certain phase transitions that arise within the Cu−S system, as will be discussed below.

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Digenite, γ-Cu2-xS, exhibits considerable variation in non-stoichiometry that extends to
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Cu1.75S at 445 °C [6]. This cubic phase has a highly disordered copper-substructure that contains a
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large fraction of closely interconnected copper vacancies, which accounts for its high ionic (Cu+)

conductivity [1]. Hexagonal β-Cu2S also has a high ionic conductivity (σCu+ = 0.2 S cm−1 at 400 °C)
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and an unusually large transference number (tCu+ ≈ 0.5) for a mixed conductor [7].

Covellite, CuS, is a p-type metal at room temperature [8] and a superconductor below 1.6 K
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[5]. CuS is essentially stoichiometric [9] and has a unique crystal structure shared only by the

selenium analogue, CuSe, with which it forms a continuous solid solution [10]. Its optical
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properties display extreme pleochroism and anisotropism under linearly polarised light [11], which
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is consistent with its two-dimensional hexagonal crystal structure (see Fig. 1). Its electronic

structure, including assignment of formal valences for the copper and sulfide ions, remains a

matter of some debate [12-18]; though recent experimental evidence indicates the presence of

mixed Cu+/Cu2+ valency with a predominance of Cu+ over Cu2+ or, a non-integral valency of

approximately Cu1.3+ which is consistent with electron delocalisation in this metallic phase [17, 18].

Information regarding the ionic conducting properties of covellite is scarce: Donner and Rickert
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[19] studied the electrochemical reaction between copper and molten sulfur at 400 °C and

concluded that the mobility of copper ions in covellite should be much lower than in digenite. Galli

and Garbassi [20] performed EMF measurements on a galvanic cell containing CuS and found that

the ionic contribution to the electrical conductivity at 25 °C was nil.

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Fig. 1. Crystal structure of covellite, CuS, emphasising the


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linkage of planar CuS3 triangles (red) with CuS4 tetrahedra


(orange). Sulfur sites are shown as yellow spheres (colour
online). Drawn using data from ICSD 61793.
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 single column fitting image 


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Covellite can be prepared by reacting copper metal with sulfur vapour at high temperature.
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This reaction occurs fairly rapidly, though not explosively, during the initial stages to form a dense

layer of digenite on the surface of the copper, whereas the subsequent reaction between digenite

and sulfur vapour to form covellite is much slower. Buckel and Hilsch [21] observed an outward

diffusion of copper during the reaction between pieces of copper and sulfur vapour at 470 °C,

resulting in an inner void and an outer CuS mantle, with an intermediate zone of Cu1.8S. These

features were attributed to an outward diffusion of Cu+ ions and electrons.


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There is a metallurgical interest in the role of copper sulfide scale as a protective coating

against the corrosive action of sulfur vapour towards copper metal. Within this context, Bruckman

and Simkovich [22] sulfurised a block of Cu2S for 20 hours in boiling sulfur, and discovered that

two distinct zones of covellite formed on its surface. Unfortunately, the micrograph of their

reaction product is of poor quality and offers little detail of the microstructure. Nevertheless, they

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concluded that during the sulfurisation of Cu2S to CuS, an outer layer of primary CuS grows by a

continuous outward movement of copper ions through this supervening layer, driven by a

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complementary loss of copper from the underlying Cu2S, which in turn, is itself, transformed into

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secondary CuS within this lower region. Lambertin and Colson [23] and Furer et al. [24-25] came to

a similar conclusion from their experiments on the sulfurisation of digenite, γ-Cu2-xS, and digenite-

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coated copper wire, using scanning electron microscopy and thermogravimetry. They discovered
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that although the kinetics evolve during the sulfurising process, as revealed by a change in
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activation energy, the diffusion of copper ions through the copper sulfide product layer was rate

determining throughout the reaction.


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In this article we study the changes in the microstructure that take place during the
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sulfurisation of digenite, γ-Cu2-xS, to covellite, CuS, under an atmosphere of sulfur vapour. The
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objective is to reassess the reaction mechanism and find evidence of copper ion mobility in

covellite at high temperature that might help identify a diffusion pathway in this stoichiometric
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phase. We exploit the strongly contrasting optical properties of covellite under linearly polarised
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light (PL) which distinguish it from digenite (and anilite, Cu1.75S) and highlight its grain structure

during the examination of polished sections of our product materials, and discuss our findings.

Moreover, we are interested in improving the efficiency of this synthesis method in order to

prepare covellite as a pure monophase material.


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2. Experimental

A series of experiments were conducted involving the sulfurisation of copper metal and

digenite, γ-Cu2-xS, in evacuated glass ampoules at high temperature as described in the following

sub-sections.

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2.1. Sulfurisation of copper rod to form a mixture of digenite and covellite

A 10-g sample of ‘Cu1.375S’, equating ideally to an equimolar mixture of Cu1.75S and CuS, was

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prepared as follows: 2.686 g of sulfur powder (technical grade, 99.9%, Sigma-Aldrich) was

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introduced into the lower compartment of a double-bulbed (∼100 and ∼200 mm in length) Pyrex™

glass tube (11 mm ID, 16 mm OD) followed by a small plug of glass wool to partially block the

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entrance to the lower compartment. A 7.314-g stack of copper rods (1 mm diameter, ∼30 mm
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long, >99.9%) were then introduced into the upper compartment. The tube was evacuated (< 10
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Pa) and sealed using an oxyacetylene torch. The ampoule was placed in an Aurora kiln P5923

(Potterycrafts Ltd) and heated at a rate of 60 oC/h to 445 °C and held there for 200 h before being
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cooled to room temperature at 100 oC/h. The product was recovered from the ampoule and
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analysed by powder X-ray diffraction (PXRD). A cross-section of the product material was
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examined by scanning electron microscopy (SEM), and a similar section set in resin for analysis by

reflected-light microscopy (RLM); see Section 2.5 for analytical details.


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2.2. Time dependency on the reaction between copper metal rods and sulfur vapour

A series of 2.7 mm diameter copper rods were sulfurised with an excess of elemental sulfur

(10 at. % S excess with respect to CuS) in sealed evacuated Pyrex™ glass ampoules (6 mm ID, 8 mm

OD) for various reaction times. These were placed in a Lenton tube furnace LTF16/50/180 with the

copper rod situated in the hot zone and heated to 420 °C at a rate of 60 oC/h. After 0.5, 1, 3, 5, 10,

20, 100, 150 and 200 h at 420±10 °C, respectively, they were cooled to room temperature at 20
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C/h. The rods were weighed before and after the reaction to compare the mass gain over time.

Furthermore, samples of the product materials were set in resin and analysed by RLM.

2.3. The preparation of a digenite, γ-Cu1.8S, ingot and its subsequent two-stage partial

sulfurisation to covellite, CuS

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An ingot of γ-Cu1.8S was prepared by reacting 5.042 g of copper with 1.407 g of sulfur inside

an evacuated quartz-glass ampoule (8 mm ID, 10 mm OD), held vertically inside a tall alumina

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crucible (Almath CC56) placed within a Lenton chamber furnace UAF15/10. The charge was first

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heated to 445 °C at a rate of 60 oC/h and held there for 24 h, before heating further to 1100 °C at

a rate of 200 oC/h. After holding the melt at 1100 °C for 2 h, it was cooled at 100 oC/h to room

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temperature. This heating profile was devised to ensure that all the sulfur had reacted with the

copper before raising the temperature to form a melt, thereby avoiding an excessive sulfur vapour
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pressure that would cause the ampoule to explode.


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Fig. 2. The polished top-end of the γ-Cu1.8S ingot before


and after the two stages of sulfurisation. Top left: polished
γ-Cu1.8S surface encapsulated in the glass tube. Top right:
first layer of CuS grown on γ-Cu1.8S at 440±10 °C. Bottom
left: first CuS layer ground flat. Bottom right: second layer
of CuS after the second sulfurisation at 440±10 °C.
 single column fitting image 
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Whilst keeping the γ-Cu1.8S ingot encased within the glass tube, the top end of the tube was

cut with a diamond saw close to the ingot and ground with appropriate grades of SiC paper,

finishing with 2400 grit, to yield a flat surface flush with the quartz-glass wall. This was placed

inside a Pyrex™ glass ampoule (11 mm ID, 16 mm OD) and reacted with 0.707 g of sulfur at 440±10

°C for 500 h in a Lenton tube furnace LTF16/50/180. This reaction formed a layer of CuS (∼1 mm

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thick) on top of the exposed digenite; unfortunately part of the quartz-glass wall had fractured and

had to be removed. The upper surface of the CuS layer was ground to create a flat surface whilst

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avoiding exposing the underlying digenite. This was reacted with excess sulfur at 440±10 °C for

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500 h in an evacuated Pyrex™ glass ampoule. Photographs of these various steps in the reaction

are shown in Fig. 2. Finally, this product was set in resin, ground and polished as a longitudinal

section, and analysed by RLM.


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2.4. A comparison of the sulfurisation of a coil of copper wire with that of copper powder

A series of copper coils (9 mm OD) made from 1 mm diameter copper wire were sulfurised
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with an excess of sulfur (50 at. % S excess with respect to CuS) in sealed evacuated double-bulbed
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Pyrex™ glass ampoules (11 mm ID, 16 mm OD) as described in Section 2.1. These dimensions
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ensured that the contact area between the copper coil and the glass wall were minimal. These

were placed with a slight incline (so that the sulfur containing bulb was at a lower level to the
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copper coil) in a Lenton chamber furnace UAF15/10 that had been pre-heated to 445 °C, and held
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for 5, 24, 48 and 72 h, respectively, before being cooled rapidly in air to room temperature; hence

these reactions are restricted to the periods at 445 °C only. The copper coils were weighed

immediately before and after sulfurisation. The product materials were analysed by PXRD. A

similar set of experiments were performed in concert under the same conditions, but using copper

powder (99.5%, <426 µm, Sigma-Aldrich) in place of the copper coils for comparison.
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2.5. Analysis

Samples of the product materials were analysed by PXRD using a Panalytical X-ray power

diffractometer with Cu-Kα radiation. High-score Plus software was used to strip reflections

attributed to Cu-Kα2 radiation and to remove the background count. Polycrystalline silicon was

used as an external standard for aligning the instrument. Samples were analysed by scanning

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electron microscopy (SEM) with a Leo SEM at 20 kV and 600 pA probe conditions. Regarding RLM,

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samples were set in resin using 40 mm diameter polypropylene moulds with EpoFix resin 3082 and

hardener 2259, then ground using appropriate grades of SiC paper and finally polished with 6, 3

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and 1 µm polycrystalline diamond spray (Struers A/S). Polished sections were examined using a

Nikon Optiphot 100S metallurgical microscope with linearly polarised light. Images were recorded

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using a Nikon DS-Fi1 digital camera with NIS-Elements F3.0 software.
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3. Results and discussion

The reaction between copper metal and sulfur vapour did not yield covellite directly, but
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instead formed digenite as an intermediate phase. The rapid diffusion of copper ions within
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digenite ensures that the growth of this phase continues and predominates until essentially all the
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copper metal is consumed. When sufficient sulfur is available in the system, the reaction then

proceeds to convert the digenite to covellite, which is the focus of our present work.
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Sulfurising a stack of 1 mm diameter copper rods at 445 °C for 200 h with a net Cu/S atomic
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ratio of 1.375 resulted in a two-phase mixture of covellite, CuS, and digenite, γ-Cu2-xS, as revealed

by PXRD (see Fig. 3) and RLM (see Fig. 4). This indicates that a cooling rate of 100 °C/h is too high

to enable the remaining γ-Cu2-xS to transform into anilite, Cu1.75S; which is reported to be the

thermodynamically stable phase in equilibrium with CuS at room temperature [26-27]. Because a

limited amount of sulfur was made available in this experiment, the transformation of γ-Cu2-xS to
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CuS is only partial, and this has resulted in a clear view of the reaction front in the product

material.
Intensity / a.u.

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10 20 30 40 50 60 70 80
2θ / degree

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Fig. 3. PXRD pattern of the product material after
sulfurising the 1 mm diameter Cu rods at 445 °C for 200 h
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with a net atomic ratio Cu:S = 1.375 (see Section 2.1).
JCPDS 6-464 for covellite (squares, green lines) and JCPDS
73-8624 for digenite, γ-Cu1.8S (circles, red lines) are shown
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for comparison (colour online).

 single column fitting image 


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The microstructure of the product material (see Fig. 4) shows that the copper has reacted
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with sulfur to form hollow copper sulfide tubes with an inner diameter of about 1 mm, which
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corresponds to the diameter of the parent copper rods. The SEM images reveal a radial growth of

crystallites, particularly in the outer region, which in certain places have collided with each other
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at the border between two separate copper rods resulting in the termination of their growth. The
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micrographs taken under linearly polarised light (Fig. 4) reveal that CuS has formed in two discrete

regions, as identified by its distinctive pleochroism (deep blue to pale blue). The outer layer of CuS

shows a strong radial alignment of densely packed platy crystallites, with a few inclusions of

γ-Cu2-xS grains in the vicinity of the underlying γ-Cu2-xS core (bluish white, isotropic). Whereas, the

layer of CuS at the inner side of the cylindrical walls reveals grains of CuS that are more randomly

oriented.
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200 µm 10 µm

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Fig. 4. Product material after sulfurising the 1 mm diameter Cu rods at 445 °C for 200 h with a net atomic ratio Cu/S =
1.375. Top left: SEM image of a freshly fractured cross-section. Top right: highly magnified SEM detail of the collision
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zone between CuS platy crystallites originating from separate Cu rods. Bottom left: Polished cross-section under
linearly polarised light revealing a mixture of digenite and covellite. Primary CuS (outer pleochroic layer of radially
aligned platy crystallites) in contact with the encapsulated digenite core (bluish white, isotropic). Secondary CuS (inner
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pleochroic layer of randomly oriented crystallites). The dark grey central voids are resin filled relics of the former Cu
rods. Width of field = 2.46 mm. Bottom right: This higher magnification of the sample on the left clearly shows the
difference in morphology of the primary and secondary CuS. Width of field = 615 µm. See section 2.1 for details.
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(Colour online).

 2-column fitting image 


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A likely mechanism is that during the course of the sulfurisation, the digenite solid-solution,
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γ-Cu2-xS, becomes saturated with sulfur to the point where it is critically deficient in copper, such

that any further addition of sulfur causes a certain fraction, (1−x)/(2−x), of the copper atoms to be

expelled from γ-Cu2-xS to form primary CuS as an external growth; whilst the now Cu-depleted

γ-Cu2-xS transforms into secondary CuS as an exsolved phase within the parent γ-Cu2-xS matrix. As

to why the secondary covellite forms initially at some considerable distance from the primary

covellite, rather than adjacent to it, is not obvious to us. Nevertheless, these phase relationships
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are consistent with the phase rule, in the sense that both covellite regions coexist in a state of

equilibrium with Cu-deficient digenite at 445 °C. In fact, the chemical potential of the copper

atoms in this two-phase material remains constant throughout this transformation, and is the

driving force for the outward diffusion of the copper ions through the digenite and secondary

covellite towards the solid/sulfur-vapour interface.

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In order to see what effect the reaction time might have on the transformation of γ-Cu2-xS to

CuS, a copper rod with a diameter of 2.7 mm was sulfurised with an excessive amount of sulfur

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vapour at 420 °C for various lengths of time (see Section 2.2 for experimental details). Since the

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heating and cooling rates add a finite time to the reaction time at 420 °C, only a qualitative

correlation of the kinetics can be derived from these experiments. Nonetheless, the mass gain as a

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function of reaction time indicates that the sulfurisation of Cu to γ-Cu2-xS at 420 °C is quite rapid
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(see Fig. 5). More importantly, Fig. 5 reveals that the initial stage of the transformation of γ-Cu2-xS
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to CuS is also fairly rapid, whereby about 50 % of the γ-Cu2-xS was transformed to CuS within 0.5 h

(excluding the heating and cooling time); although it appears that a full transformation needs
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about 100 h for a copper rod with this diameter.


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Fig. 5. Percentage mass increase of the product material


with respect to Cu as a logarithmic function of the
sulfurisation time at 420±10 °C. The red line and band
serve as guides to the compositions of CuS and γ-Cu2-xS
respectively. See section 2.2 for details.
 single column fitting image 
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Fig. 6. Polished sections of product materials under linearly polarised light after reacting a 2.7 mm diameter Cu rod
with excessive sulfur at 420±10 °C for 0.5 h (left), and 150 h (right). Heating and cooling rates were 60 °C/h and 200

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°C/h, respectively, in both cases. Left longitudinal-section: primary CuS (upper coarse grained outer pleochroic layer)
in contact with the parent γ-Cu2-xS (bluish white); secondary CuS (lower fine grained inner pleochroic layer). Right
cross-section: primary CuS (outer pleochroic layer of platy crystallites) in contact with secondary CuS (finer grained

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inner pleochroic layer with a mottled appearance). The dark grey voids (bottom) are resin filled relics of the former Cu
rods. Width of field = 2.46 mm. (Colour online).
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 2-column fitting image 
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These results are consistent with the corresponding micrographs shown in Fig. 6, which

show polished sections of the reaction product after reaction periods of 0.5 and 150 h,
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respectively. From Fig. 6 (left) it can be seen that a reaction period of 0.5 h resulted in a
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substantial growth of primary CuS with a strong radial alignment of platy crystallites, which is in
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direct contact with the parent γ-Cu2-xS; whereas the CuS grains at the inner side of the cylindrical

wall are considered to be secondary CuS. Furthermore, in Fig. 6 (left) it can be seen that almost
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50% of the γ-Cu2-xS has transformed to CuS. From Fig. 6 (right) it can be seen that after a reaction
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period of 150 h essentially all the γ-Cu2-xS has transformed to CuS, with roughly equal areas (or

volumes) of primary and secondary CuS. The primary CuS shows strong radial alignment in which

the platy crystallites span about half the width of the wall, and come in contact with the secondary

CuS which has smaller and more randomly oriented grains that create a mottled appearance.
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Fig. 7. Polished cross-section of the product material after
two consecutive reactions of the exposed top-end of the
digenite ingot with sulfur at 440±10 °C. The resin block is
40 mm in diameter. The area outlined in white
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corresponds to the detail in Fig. 8. See section 2.3 for


details. (Colour online).

 single column fitting image 


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Fig. 7 shows the polished longitudinal cross-section of the γ-Cu1.8S ingot after reacting the
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accessible top-end of the ingot with sulfur vapour at 440±10 °C in a two-stage partial sulfurisation
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to covellite, as described in Section 2.3. Note that the area outlined in white in Fig. 7 corresponds
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to the micrographs in Fig. 8. From Fig. 7 it is evident that covellite has formed not only at the top-

end, as was intended, but around its entirety. This is a side effect due to the fact that the glass

surrounding the γ-Cu1.8S ingot had cracked after the first sulfurisation experiment, enabling sulfur

vapour to react with other parts of the ingot during the second sulfurisation. Fortunately, this did

not jeopardise the main purpose of the experiment.


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2nd layer

1st layer

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Original
γ-Cu1.8S

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Fig. 8. Polished section of the product material after two consecutive reactions of the exposed end of the digenite
ingot with sulfur vapour at 440±10 °C. Left: under linearly polarised light, revealing a large covellite grain (blue, centre)

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next to a digenite grain (bluish white, centre far-right); parent digenite (bluish white, bottom). Right: under crossed-
polars, isotropic digenite is in extinction and thus appears black, as do certain covellite grains (centre left) where their
c-axis is oriented perpendicular to the plane of view. Width of field = 2.46 mm. (Colour online).

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 2-column fitting image 
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The sulfide layer near the bottom in Fig. 8 comprises small irregular-shaped grains of CuS
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interspersed within the parent digenite matrix, and these are interpreted as secondary covellite. In
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contrast to this, the boundary between the first and second layer of primary covellite is quite
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distinct in this section, and is highlighted by the presence of larger grains in the first layer.

Moreover, the second layer is merely a quarter of the thickness of the first layer, which indicates
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that the flux of copper ions at the solid/sulfur-vapour interface were greater during the first
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reaction between γ-Cu1.8S and sulfur, than in the second stage. These results are consistent with
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the hypothesis that the rate of reaction is dependent on the outward diffusion of copper ions

through the primary covellite. Furthermore, the fact that the second layer of primary CuS has

grown directly on top the first layer, excludes the possibility of the counter mechanism, in which

sulfur diffuses inwards through the primary CuS layer and reacts with the underlying γ-Cu1.8S at

the γ-Cu1.8S/CuS interface.


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It is quite likely that the odd digenite grain within the first primary CuS layer (cf. Fig. 8)

formed during the first sulfurisation stage at 445 °C. During the actual sulfurisation the system is

expected to be in a state of non-equilibrium, but once the partial sulfurisation is finished, the

system, whilst still hot, relaxes towards a state of equilibrium in which covellite coexists with Cu-

deficient digenite; i.e., γ-Cu1.75S at 445 °C [6]. This would cause a small fraction of the copper ions

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in the original γ-Cu1.8S ingot to diffuse into some of the neighbouring CuS grains, thereby

transforming them to γ-Cu1.75S, whilst their own composition adjusts to γ-Cu1.75S. This process will

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cease once all the digenite in the ingot has obtained the equilibrium composition, γ-Cu1.75S. This

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feature will not arise during the formation of the second primary CuS layer, since the composition

of the digenite has by now equilibrated. In hindsight it would be wiser to have had an ingot

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prepared with the composition γ-Cu1.75S, to avoid this situation.
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All in all the above results demonstrate that copper ions can diffuse through covellite at high
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temperature (445 °C), and that covellite is considerably less ionically conducting than digenite.

This disparity is likely to be a consequence of the differences in the crystal and defect structure of
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these two phases. Although the mechanism for Cu+ ion conduction in digenite has been described
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in the literature (as summarised in the Introduction section), the possible copper ion conduction
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pathways in covellite have been largely overlooked. One of us has reported elsewhere [15] that

the copper ions in the CuS4 tetrahedra should be the less strongly bound to sulfur than the copper
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ions in the planar CuS3 triangles (based on a comparison of bond lengths [18]) and therefore can
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be expected to be the more mobile of the two. The question then arises as to which pathway

through the covellite structure is most viable.

One possible route is via the neighbouring S–S interspatial layer of interconnected trigonal

prismatic intersticies (see Fig. 1) [15]. On first inspection this looks like an intercalation plane that

might prove ideal for the copper ions to move through; but the S–S interplanar spacing is very

narrow at 207 pm [28], i.e., shorter than the S–S covalent bond in orthorhombic sulfur. Whereas
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the larger pores that lie in the plane of the CuS4 tetrahedra should provide a more realistic

pathway to facilitate the cooperative migration of copper ions between adjacent CuS4 tetrahedra.

This model would imply that copper ion mobility is restricted to within the basal plane, in a similar

way to the Na+ ions in the 2-dimensional ion conductor, sodium β-alumina. It would also explain

why the covellite in the primary layer forms platy crystals that are aligned with their hexagonal

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basal plane parallel to the direction of the outwardly diffusing copper ions.

In this context, it is interesting to note that Saito et al. [29] discovered a similar texture (as

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characterised by PXRD) in which the c-axis of their covellite crystals were preferentially aligned

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parallel to the longitudinal direction of a pre-stretched copper wire. The only difference is that in

our experiments we did not need to pre-stretch the copper wire to obtain a similar effect.

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Furthermore, the alignment in our material was limited to the primary covellite that occurs in the
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outer layer. Saito et al. [29] did not differentiate between primary and secondary covellite in their
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material because their samples were not characterised microscopically, and so a further

comparison is impossible. Even so, it is difficult to see how this alignment could be dependent on
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the history of the copper wire as inferred by Saito et al. [29], given that it first forms digenite as an
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intermediate phase, where any feature inherited from the metallic copper would surely be lost by
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the time the digenite transforms into covellite. From our results, we infer that this crystal

alignment is a consequence of copper ion mobility being restricted to within the basal plane of the
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covellite structure, which provides the principle source of copper ions (as supplied from the
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underlying digenite) for the propagation of crystal growth in this same planar projection, thereby

resulting in a radiating stack of platy crystals, as seen in Figs. 4 and 6.

Regarding the oxidation state of the mobile copper ion, the possibility of mixed Cu+/Cu2+ or a

non-integral valency of approximately Cu1.3+ in covellite was referred to in the Introduction

Section. Therefore it is interesting to note that since Cu+ is a highly polarisable ion, the mobile Cu+

ions could intermediately change their valence to smaller divalent Cu2+ ions during transport,
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which might assist their movement through certain bottle-necks in the covellite structure. A

similar mechanism implicating the transient existence of Cu2+ ions in the activated state (via a

reversible charge-transfer process, i.e., Cu+ ⇌ Cu2+ + e−), has been proposed by Warner and Maier

[30] to account for the temperature-independent transference number of the copper ions within

the mixed (Cu+/e−) conductor, Cu2Mg3(PO4)3. Given the non-integral nature of the oxidation state

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of the copper ions in CuS, a similar mechanism could also apply here. But most explicitly, whatever

the true nature of their oxidation state, we have demonstrated that copper ions can diffuse

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through covellite at 445 °C at a moderate rate.

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Fig. 9. Percentage mass increase of the product material


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with respect to Cu as a function of the sulfurisation time at


445 °C for Cu wire coil (circles) and powder (squares). The
red line and band serve as guides to the compositions of
CuS and γ-Cu2-xS respectively. See section 2.4 for details.
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 single column fitting image 


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From the above results it is clear that the morphology of the digenite intermediate material

is a crucial factor in the efficiency of preparing covellite by this high temperature method.

Therefore a coil of copper wire should over time prove more reactive towards sulfur vapour than a

charge of copper powder, when preparing CuS. Thus a series of sulfurisation experiments were

performed to compare these two forms of copper as described in Section 2.4. Fig. 9 shows the
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gain in mass of the product material as a function of reaction time with sulfur vapour at 445 °C.

Although the copper powder reacted quite rapidly with sulfur vapour at 445 °C to form digenite

within 5 h, the digenite crystallites sintered into an agglomerate which retarded its subsequent

transformation to covellite, such that this was still incomplete after 72 h. On the other hand,

sulfurising a coil of copper wire produced a corresponding hollow coil of digenite that retained its

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open morphology and was mechanically stable (see Fig. 10). Evidently, this larger surface-area to

volume ratio has enabled the digenite to react more efficiently with sulfur vapour to form

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monophase covellite within 24 h, and in a physical form that is easier to retrieve from the glass

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ampoule.

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Fig. 10. Glass ampoule containing a coil of 1 mm diameter Cu wire before (top) and after (bottom) sulfurising at 445
°C for 48 h to yield monophase CuS.
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 2-column fitting image 


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4. Conclusions
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The results from a controlled two-stage partial sulfurisation of digenite, γ-Cu1.8S,

demonstrate for the first time that covellite, CuS, in addition to being a p-type metal, is ionically

conducting at 445 °C, although considerably less so than digenite. This may have implications for

workers developing Cu-S based photovoltaic materials, where they should be aware of moderate

ionic conductivity in covellite at high temperature in the fabrication of their devices.


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We have shown that two discrete regions of covellite (denoted as primary and secondary)

form during the sulfurisation of digenite by separate but interrelated mechanisms, which is

consistent with the work by Bruckman and Simkovich [22], and that this accounts for the

differences in their texture. We infer that the growth of platy covellite crystals and their radial

alignment in the primary CuS layer are the consequence of copper ion mobility being restricted to

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the hexagonal basal plane of the covellite structure.

This work has also shown, in the context of corrosion, that the formation of digenite offers

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no protection to the copper metal from sulfurisation at 445 °C. The outer covellite layer retards

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the subsequent sulfurisation of the underlying diginite to some degree, on account of the slower

diffusion of copper ions through this stoichiometric phase. Nevertheless, by this stage in the

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corrosion, most, if not all, of the copper metal is likely to have already been consumed by the
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sulfur in the process of forming digenite.
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Furthermore, we have devised a more effective and reliable method for synthesising

covellite as a monophase material from its elements that involves reacting a coil of copper wire,
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rather than copper shot, rod or powder, with sulfur inside an evacuated glass ampoule. This
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method may prove beneficial for the preparation of other metal sulfides, as well as complex metal
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sulfides such as ternary thiospinels, by sulfurising a coil of the corresponding alloy at high

temperature.
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Acknowledgements

The authors are grateful to Jeanette Hvam for assistance with the scanning electron

microscopy, and to Torben H. Jensen and Danny Kyrping for technical assistance with the furnaces.

The authors also thank Peter Brilner Lund and Per Morgen for reading and commenting on the

typescript. This research did not receive any specific grant from funding agencies in the public,

commercial, or not-for-profit sectors.


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References

[1] M.E. Fleet, Phase equilibria at high temperature, in: D.J. Vaughan (Ed.), Sulfide Mineralogy

and Geochemistry, The Mineralogical Society of America, Virginia, 2006, pp. 365−419.

[2] K.L. Chopra, S.R. Das, Thin Film Solar Cells, first ed., Springer, New York, 1983.

[3] J.B. Wagner, C. Wagner, J. Chem. Phys. 26 (1957) 1602−1606.

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[4] Y. Fu, A, Manthiram, Electrochim. Acta 109 (2013) 716−719.

[5] W. Meissner, Z. Phys. 58 (1929) 570−572.

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[6] P.B. Barton, Econ. Geol. 68 (1973) 455−465.

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[7] E. Hirahara, J. Phys. Soc. Jpn. 6 (1951) 428−437.

[8] H. Nozaki, K. Shibata, N. Ohhashi, J. Solid State Chem. 91 (1991) 306−311.

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[9] G. Kullerud, Carnegie Inst. Yearbook 57 (1958) 215−218

[10] M. Ishii, K. Shibata, H. Nozaki, J. Solid State Chem. 105 (1993) 504−511.
M

[11] J.R. Craig, D.J. Vaughan, Ore microscopy and ore petrography, second ed., Wiley, New York,
D

1994.
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[12] I.I. Mazin, Phys. Rev. B 85 (2012) 115133.

[13] S.W. Goh, A. N. Buckley, R.N. Lamb, Miner. Eng. 19 (2006) 204–208.
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[14] A. Morales-García, A.L. Soares, E.C. Dos Santos, H.A. de. Abreu. H.A. Duarte, J. Phys. Chem. A

118 (2014) 5823−5831.


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[15] T.E. Warner, Synthesis, Properties and Mineralogy of Important Inorganic Materials, first ed.,
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Wiley, Chichester, 2011.

[16] G. van der Laan, R.A.D. Pattrick, C.M.B. Hendersen, D.J. Vaughan, J. Phys. Chem. Solids 53

(1992) 1185–1190.

[17] S. Conejeros, I. de P.R. Moreira, P. Alemany, E. Canadell, Inorg. Chem. 53 (2014)

12402−12406.
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[18] R.R. Gainov, A.V. Dooglav, I.N. Pen’kov, I.R. Mukhamedshin, N.N. Mozgova, A.V. Evlampiev,

I.A. Bryzgalov, Phys. Rev. B 79 (2009) 075115.

[19] D. Donner, H. Rickert, Z. Phys. Chem. 60 (1968) 11−24.

[20] R. Galli, F. Garbassi, Nature 253 (1975) 720−722.

[21] W. Buckel, R. Hilsch, Z. Phys. 128 (1950) 324−346.

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[22] A. Bruckman, G. Simkovich, Corros. Sci. 12 (1972) 595−601.

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[23] M. Lambertin, J.-C., Colson, Oxid. Met. 7 (1973) 163−171.

[24] J. Furer, M. Lambertin, J.-C., Colson, Mat. Res. Bull. 10 (1975) 1047−1054.

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[25] J. Furer, M. Lambertin, J.-C., Colson, Corros. Sci. 17 (1977) 625−632.

[26] P. Franke and D. Neuschütz, Binary System Cu-S in Landolt-Börnstein: Group IV, Physical

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Chemistry, Volume 19B3 Binary system Part 3, Springer, Berlin Heidelberg, 2005.

[27] D.J. Chakrabarti and D.E. Laughlin, Bull. Alloy Phase Diagr. 4 (1983) 254–271.
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[28] H.T. Evans, J.A. Konnert, Am. Miner. 61 (1976) 996−1000.

[29] S.H. Saito, H. Kishi, K. Nie, H. Nakamaru, F. Wagatsuma, T. Shinohara, Phys. Rev. 55 (1997)
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14527−14535.

[30] T.E. Warner, J. Maier, Mater. Sci. Eng. B 23 (1994) 88−93.


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Supplementary material for Fig. 6 (right)

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Polished cross-section of the product material under linearly polarised light after reacting a 2.7 mm diameter Cu rod
with excessive sulfur at 420±10 °C for 150 h. Heating and cooling rates were 60 °C/h and 200 °C/h, respectively, in
both cases. Primary CuS (outer pleochroic layer of platy crystallites) in contact with secondary CuS (finer grained inner
pleochroic layer with a mottled appearance). The dark grey void (bottom) is a resin filled relic of the former Cu rod.
Width of field = 2.46 mm. Top: as shown in manuscript. Middle: polariser set 90 degree with respect to top image,
showing pleochroism characteristic for covellite. Bottom: crossed polars, showing anisotropy characteristic for
covellite.