NANO-PARTICLE PRODUCTS FROM NEW
MINERAL RESOURCES IN EUROPE
– ProMine –
WP 3
NEW NANO-PRODUCTS FROM MINERAL
EXPLOITATION
New rhenium-based products for demanding
applications
Levi, April 2013
Spherical rhenium and its alloys
 Partners
involved:
KGHM ECOREN - Polish Industry
INSTYTUT METALI NIEZELAZNYCH (INSTITUTE OF
NON-FERROUS METALS) - R&D Centre
Rhenium
-
one of the rarest elements in nature
-
content in the Earth's crust is estimated at the level of 10-7 %.
-
mainly extracted from copper-molybdenite ores
-
often recovered from dusts and gases generated in
molybdene roasting plants.
-
world rhenium resources at the level of 11-17 thousand tons
-
production in 2012 was about 60 tons
Rhenium
-
in its solid state rhenium is a ductile material,
-
presents high hardness,
-
high melting point (3,180 °C)
-
and high density (21.0 g/cm3).
-
applied in:
- heat-resistant alloys – used in heating components of
electronic equipment
- production of superalloys
Superalloys
-
high mechanical and thermal strength,
-
used in production of rocket engine nozzles and rotating components in
aircraft engines and in energy equipment
-
contain over 50 % of nickel as well as chromium, cobalt, tantalum,
aluminium, molybdenum, tungsten, titanium, hafnium and rhenium.
-
rhenium addition in the amount of 3 to 6 % brings both better engine
performance and fuel saving.
-
currently supperalloys represent 77 % of rhenium demand
Aim of work
The development of 2 new types of products for
applications in high-tech materials, such as superalloys
and thermal barrier coating :
- spherical powder of metalic Re
-
rhenium alloys: Re-Co and Re-Ni powders and pellets
Superalloy sector consumes
almost 80% of rhenium global
production
A 2010 ROSKILL REPORT
Rhenium resources




Rhenium content in the Polish copper concentrates is at
the level from 5 to 15 ppm.
The concentrates are processed by KGHM Polska Miedz
S.A. in three copper smelters, i.e.: Glogow I smelter,
Glogow II smelter and Legnica smelter.
Because of high volatility of the oxidised rhenium forms
(especially dirhenium heptoxide) rhenium accumulates in
dusts and gases during pyrometallurgical treatment of
copper concentrates
Five materials of increased rhenium content can be
identified, i.e. three washing acids, secondary dusts from
lead metallurgy and Fe-As alloy (speiss).
Spherical powder rhenium should have lower porosity, higher
density, better liquidity, greater durability and purity, when
compared to classical powder.
The alloys, when compared to the alloys produced by powder
metallurgy methods from mixture of pure metals powders,
should have lower impurity content and higher homogeneity,
and should provide possibility for elimination of currently used
toxic carbonyls in the production process.
The production process consists of two stages:
 hydrometallurgical process for production of relevant
perrhenates
 powder metallurgy for production of alloys and
spheroidization
In the development of the procedures for production of perrhenates of
selected metals as the initial raw material ammonium perrhenate(VII)
was used, produced by KGHM Ecoren S.A. – especially purified for the
needs of this project
Composition of NH4ReO4 (99.99 % purity): Re > 69.40 %
Ca < 0.0005 %, K < 0.001 %, Mg < 0.0005 %, Cu < 0.0005 %,
Na < 0.0005 %, Mo < 0.0005%, Ni < 0.0005 %, Pb < 0.0005 %,
Fe < 0.0005 %
Production of rhenium compounds by
hydrometallurgical methods
Perrhenic acid was used as a source of rhenium for
production of perrhenates of selected metals. The perrhenic
acid was produceted by ion-exchange method form high
purity ammonium perrhenate. The ammonium perrhenate of
purity 99,99 % - produced by KGHM Ecoren S.A. – ProMine
consortium partner.
We studied 3 method of production of perrhenates:
• classical method
• ion-exchange method
• solvent extraction
Idea of investigation using clasical method
REACTION
anhydrous Ni(ReO4)2
66.60 % Re and 10.50 % Ni
FILTRATION
anhydrous Co(ReO4)2
EVAPORATION
66.60 % Re and 10.50 % Co
DRYING
PRODUCTS
Process efficiency > 99 %
Idea of investigation using ion exchange method
CONDITIONING
WASHING
anhydrous Ni(ReO4)2
66- 68 % Re and 7-10 % Ni
SORPTION
WASHING
ELUTION
anhydrous Co(ReO4)2
66-68 % Re and 7 -10 % Co
EVAPORATION
DRYING
PRODUCTS
Process efficiency > 99 %
Investigation using solvent extraction method
EXTRACTION
WASHING
STRIPING
WASHING
EVAPORATION
DRYING
PRODUCTS
The studies showed that application
of solvent extraction for production of
nickel or cobalt and rhenium containing
solutions is inefficient because of low level
of nickel and cobalt stripping with aqueous
perrhenic acid solutions. Based on that the
method was rejected.
Comparison of the methods
Parameters
Number of operations
Solid waste amount
Liquid waste amount
Rhenium resource consumpt
Nickel resource consumption
Energy consumption
equipment
Process efficiency
Ion exchange method
7
low
high
high
stoichiometric
716 kWh / 1000 kg
columns, vacuum
evaporator, drier
>99%
low
Classical method
4
high
low
stoichiometric
high
170 kWh / 1000 kg
neutralisation reactor,
vacuum evaporator,
drier
> 99%
Purity of Ni resources
(potential for utilisation of
industrial solutions)
high
Purity of produced perrhenates
high
low
Powder metallurgy method for production
of spherical powder of Re and rhenium
alloys and rhenium alloys pellets
Examination methods:
•
Phase analysis of the samples was made by X-ray diffraction
in room temperature.
•
Studies into chemical composition in microsections and SEM
observations were made with Jeol X-ray micronalayser
JXA- 8230.
•
Density of materials was measured with Micromeritics
Accupyc 5500 instrument. Specific surface was determined
by BET method with Micromeritics Gemini 2360 unit.
•
Grain size distribution was determined by sedimentation
method with Micromeritics SediGraph 5100 instrument and
by diffraction of laser beam with Fritsch Analysette 22
Nanotec instrument.
•
Hardness was determined by Rockwella (HRA) method with
diamond cone and the load of 613 N.
Technological operations:
• Reduction
Reduction was conducted in hydrogen atmosphere for 1 hour in temperature of:
- 8000C for ammonium perrhenate
- 9000C for nickel, cobalt perrhenates
•
Mechanical synthesis
Mechanical alloying was done in Retsch planetary mill PM 400 in tungsten carbide
containers under following conditions:
- rotational speed 200 rpm.
- alloying time 1, 5 and 10 h
- diameter of WC balls 8 mm
- ball to powder mass ratio 10:1
- liquid environment: acetone
Powders of pure metals were used in production of reference materials
for the materials produced by reduction.
• Consolidation and sintering
Powder materials were consolidated
by uniaxial compaction with pressure
of 600 MPa. Sintering was performed
in hydrogen atmosphere for 1 hour in
temperature of 11500C.
• Spheroidization
Powders produced by reduction were
subjected to spheroidization with FST
AP-50 plasma system of 50kW torch
type 7MB in reaction column and
argon atmosphere.
initial powder
coarse fraction
fine fraction
Morphology of Re powder: initial powder, coarse and fine fraction after APS 79 process
Checking of the products against
specification
Physical properties of rhenium and rhenium based materials
Material
Re frayed
Reduction
ρ[g/cm3] a [m2/g]
n [µm]
19.49
>150
0.7
Spheroidization
ρ[g/cm3] a [m2/g]
n [µm]
Re APS 79
19.01
0,1
<100
Re APS 80
19.91
0.13
<100
Re APS 81
19.49
0.23
<100
Re APS 82
18.07
0.31
<100
Re APS 83-85
20.01
0.12
<100
ReNi frayed
16.48
-
<150
ReNi APS 90
13.83
-
<100
ReNi APS 91
14.42
-
<100
ReCo frayed
15.01
-
<150
ReCo APS 93
16.53
-
<100
ReFe frayed
15.07
ReFe APS 93
<150
-
17.79
<100
Specification
ρ[g/cm3] a [m2/g]
n [µm]
20-21
0.06-0.3
<150
15-17
-
<150
15-17
-
<150
14-17
-
<150
Chemical composition of Re powders
Material
Re
specification
Re initial
Re APS
83,84,85
Bi
1
Zn
50
Co
100
Mg
100
Mn
20
Mo
50
Ni
20
Pb
2
K
50
Se S
5
20
Na
10
Ca
5
Fe
100
<1
<1
4
26
<5
<5
4.8
<3
<3
<3
21,5
<5
<5
38.4
<5
<5
20
<10
<1
<1
7.6
8.9
<3
19.2
11.6
30.5
Chemical composition of Re-Co powders
Chemical composition of Re-Ni powders
Material
Specification
ReNi
ReNi APS 90
ReNi APS 91
Re [%]
85-88
86.37
93.70
90.20
Ni [%]
12-15
13.48
4.78
6.33
Mg
0,2%
7.3
-
<5
20.2
Cu
250
<3
-
Material
Specification
Re-Co
ReCo APS 93
Re [%]
85-88
86.23
92.4
Co [%]
12-15
13.62
6.44
Mg
Cu
0.2% 250
9.0
4.0
Results
1. Application of reduction process and plasma spraying leads to
production of rhenium powder which meets specification requirements
both with respect to its physical properties and chemical composition.
To produce material composed of spherical fraction mostly and
presenting the required density it is necessary to perform three
operations of spraying.
2. Ni and Co containing alloy powders, which meet the requirements as
described in the specification, are produced in a frayed form after
reduction process.
3. The sintered Re-Ni and Re-Co materials produced from the powders
generated in reduction of perrhenates show higher density and
hardness than the materials produced by mechanical synthesis.
4. Materials produced by reduction are less susceptible to impurities than
those produced by mechanical synthesis which introduces impurities
from milling bodies and containers, e.g. tungsten carbide.
Conclusions – Go/No Go decision
After thorough analysis of the results and discussion
between Ecoren and IMN it was decided that the
products which pass go/no go decision and,
therefore, should be selected to verify laboratory
scale results in larger scale are:
- spherical rhenium
- Ni-Re alloy in a form of pellets
- Co-Re alloy in a form of pellets
Piloting
Spherical powder of metallic Re
PRODUCTION OF SPHERICAL RHENIUM POWDER
NH4ReO4
NH4ReO4 REDUCTION
rhenium powder
SIEVING OF FRAYED
POWDER Re
rhenium
fraction
powder
below 100µm
PLASMA SPRAYING OF
POWDER
spherical rhenium powder
Equipment of pilot instalation

furnace operating in
hydrogen atmosphere


sieve with sub-sieves
Plasma system
PROCESS PROGRESS
500g of spherical Re powder was produced
and transferred to Ecoren
SPECIFICATION OF PRODUCTS :
Physical properties of Re powder
Density
[g/cm3]
Mean
grain size
[µm]
Grain size by
specification [µm]
20.14
10
<100
Chemical composition of Re powder
Bi
Zn
Co
Mg
Mn
Mo
Ni
Pb
K
Fe
<1
ppm
11
ppm
<5
ppm
<3
ppm
<3
ppm
<5
ppm
64
ppm
9
ppm
7
11
ppm ppm
Se
S
Na
Ca
<1
ppm
<5
ppm
12
ppm
<3
ppm
Rhenium alloys
PRODUCTION OF ALLOY POWDERS
NH4ReO4
HReO4
Ni(ReO4)2
Co(ReO4)2
powder of Re-Ni
powder of Re-Co
pellets of Re-Ni
pellets of Re-Co
EQUIPMENT OF PILOT INSTALLATION
EQUIPMENT FOR PRODUCTION OF NICKEL(II) OR COBALT(II)
PERRHENATE
reactor with mechanical agitator
vacuum nutsche filter
EQUIPMENT FOR PRODUCTION OF NICKEL(II) OR COBALT(II)
PERRHENATE

ion-exchange column
 vacuum evaporator
•

EQUIPMENT FOR PRODUCTION OF Re-Co AND Re-Ni ALLOYS
furnace operating in hydrogen atmosphere
for production of powder and pellets
•
EQUIPMENT FOR PRODUCTION OF Re-Co AND Re-Ni ALLOYS
 hydraulic press for powder consolidation
PELLETS
PROCESS PROGRESS
production of nickel(II) perrhenate: 2750g
production of Re- Ni alloy :
 1 kg pellets
 1 kg powder ( to meet demand of Ecoren clients)
SPECIFICATION OF PRODUCTS :
Physical properties of Re - Ni
Form
Density
[g/cm3]
Grain size [µm]
Powder
16.70
<100
Pellet
13. 24
-
Chemical composition of Re - Ni
Form
Powder
Pellet
Re%
86,4
85.0
Ni%
13,6
13.7
Bi ppm
<2
<2
Mg ppm
<3
<5
Cu ppm
<3
54
K ppm
<10
-
Se ppm
<2
<2
Na ppm
6,3
-
S ppm
33
42
Fe ppm
59
-
 X-ray pattern of Re-Ni pellet
 Surface distribution of elements in Re-Ni pallet
SEI
Re
Area
Re [wt% ]
Ni [wt%]
Bright matrix
88.8
11.2
Dark precipitates
31.3
68.7
 Chemical composition in microsections of Re-Ni pellet
COMP
Ni
PROCESS PROGRESS
production of cobalt(II) perrhenate: 3,400g
production of Re- Co alloy :
 1 kg pellets
 1 kg powder (to meet demand of Ecoren clients)
SPECIFICATION OF PRODUCTS :
Physical properties of Re - Co
Form
Density
[g/cm3]
Grain size [µm]
Powder
14.3
< 100
Pellet
10.1
-
Chemical composition of Re - Co
Form
Re%
Co%
Powder
Pellet
86.0
85.3
14.0
14.0
Bi ppm
<2
<2
Mg ppm
11
8
Cu
ppm
9
23
K ppm
Se ppm
Na ppm
S ppm
Fe ppm
24
<10
<2
<2
19
30
24
22
36
57
 X-ray pattern of Re-Co pallet
 Surface distribution of elements in Re-Co pallet
SEI
Re
Area
Matrix
Dark precipitates
Re [wt% ]
89.5
86.7
Co [wt%]
12.4
14.4
 Chemical composition in microsections of Re-Co pallet
COMP
Co
SUMMARY OF PILOTING
500g of spherical Re powder was produced in the constructed installation for
production of spherical powder of metallic rhenium
2 kg of Re- Ni alloy was produced in the constructed installation for production
of Re-Ni alloy :
1 kg pellets and 1 kg powder
2 kg of Re- Co alloy was produced in the constructed installation for
production of Re-Co alloy :
1 kg pellets and 1 kg powder
500 g spherical powder of Re and 1 kg Re-Ni pellets and 1 kg Re-Co
pellets were transferred to Ecoren
Patents applications (made in April 2013)





Method for production of anhydrous cobalt(II)
perrhenate(VII)
Method for production of anhydrous nickel(II)
perrhenate(VII)
Spherical Re-Co alloying powder of high rhenium content
Spherical Re-Ni alloying powder of high rhenium content
Method for production of Re-Co master alloys for
superalloys
LIST OF END-USERS CONTACTED FOR FINAL PRODUCTS TESTING
1.
2.
3.
4.
5.
6.
7.
8.
9.
Rolls Royce
GE Aviation
Cannon Muskegon
Starck
Heraeus
Pratt&Whitney
Johnson Matthey
Siemens
Polish Aeronautical Technology
Platform
Thank you for your attention