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Professional Development

Process Mineralogy
for Metals

Part 1 - Process Mineralogy and


Techniques
Introduction
The Demand for Minerals

Steps in an engineering process. Yellow arrows represent a transformational process.

Raw materials for an engineering process. Arrows indicate transformation processes.

Raw materials must be seen from the perspective of local availability and market needs.
Mining engineers must be prepared to see beyond the mining viewpoint and apply mineral
process techniques to transform any kind of raw materials (including garbage) into saleable
products.
Mining engineers must be familiar with the uses of raw materials in different industrial
sectors to be able to adapt, modify and create new uses.
A holistic vision will also help to address concerns about the environment.
"Ore is a mineral from which it is possible to produce metal by using technological
methods that already exist or can reasonably be developed. By convention there is no "clay
ore" or "gypsum ore". Minerals become ores when technological developments allow them
to be mined and treated successfully." Jones (1987)

Raw material can be evaluated:

by source, either primary sources or recycling

by the nature of the source, either renewable or non-renewable

by the final use of the material, either structural (pieces, objects, ...) or functional
(electronic, magnetic, optical, biomaterials, etc.)

Technology is used to transform raw material (minerals, metals, ceramics, plastics,


composites, wood, leather, cotton, garbage, etc.) to fulfill a market need.

Raw material will be transformed based on market needs and available technology.

Process Mineralogy Definition


"Process mineralogy which combines mineralogy and petrography with process
development engineering generates data for commercial design of the ore processing
plant."
Schapiro et al. (1981)
"Many metallurgists appreciate the importance of applied mineralogy to a much
larger extent than some geologists, who regard the study of minerals as a subsidiary
subject necessary only for a degree of geology. Unfortunately, many promising
prospects have been missed because the basic training of the person who discovered
them did not include a sound knowledge of mineralogy."
Liebenberg (1970)

Process mineralogy combines mineralogical techniques with mineral process unit operations
to identify minerals, their associations and characteristics in order to:

design processing flowsheets

specify raw materials and marketable products

troubleshoot plants, predict reagent consumption

indicate new uses of minerals

establish feasibility concepts at the early stages of geological exploration

Importance of Process Mineralogy


"Technology is whatever is needed to transform resources into products."
Even if geology and mineralogy are similar, mineral deposits are different. Technology used
in one deposit must be adapted or modified to be used in other similar deposits.
We mine rocks but we concentrate minerals (with the exception of dimension rocks and
materials for civil construction -- this actually represents more than 60% of the worldwide
mined products).
We sell and use minerals or mixture of minerals. They have characteristics and specifications
that make them saleable. If these specifications are not met, the mineral product is worthless.
Information in geological reports is not quite adequate for the next step of a mining project,
evaluating:

which valuable minerals can be concentrated

which contaminants will be together (penalties)

which technology is available and suitable for that ore

what impact it could have on the environment

which market the product is suitable for

how much will be spent to produce saleable mineral products

Process mineralogy will not provide all the answers but will give good hints at the early
stages of a geological exploration project.

Process Mineralogy Usefulness


Process mineralogy has been defined as ... "Application of a series of tools and techniques to
identify and adapt the quality of the raw material to the market needs." These tools and
techniques can:
. Characterize raw material quality
. Predict quality of concentrates and final products
. Design preliminary process flowsheets
. Provide quality control
. Add value to orebody information
. Enhance decision making
. Predict environmental impacts
. Find new applications and new products
. Indicate new markets
. Investigate recycling options

. Identify the ore-gangue associations


. Determine liberation of ore-minerals
. Quantify minerals
. Indicate (possible) losses
. Indicate by-products
. Identify available raw materials (and wastes)
. Assist technology development
. Predict raw material processing performance
. Predict reagent consumption
. Provide hints about hydro and pyrometallurgical reactions
Process Mineralogy is also known as:
. Technological Characterization
. Applied Mineralogy
. Industrial Mineralogy
. Mineralurgie

Techniques, Analysis and Classification


Main Techniques Applied to Process Mineralogy
The main techniques applied to process mineralogy depend on whether we analyze:

ores (small amount of the metallic mineral of interest: with exception of Fe and Mn,
ore-minerals occur in ore deposits in small quantities, usually < 20%; e.g. metal grades of
some ore deposits: 0.4% Cu, 12% Zn, 7% Pb, 4% Ni, 3 ppm Au, 50 ppm Ag.), or

industrial minerals (small amount of impurities; in spite of properties being related


to the chemical and mineralogical composition, quite often just performance is
investigated)

Important pieces of information are:

Representative sample (which should have similar characteristics to the mineable


material)

Mineralogy (identification and quantification of minerals are important to establish


technological routes for concentration and/or leaching, type and amount of concentrates,
quality of tailings, etc.)

Element distribution in minerals and sized fractions (gives indication about what
are the substance-bearing minerals, mineral liberation and how mass can be eliminated)

Mineral factors (characteristics and properties of minerals determine the


technological routes, mineral liberation and predict quality of concentrates)

The bottom line is to predict and explain performance when a mineral is subjected to a
physical or chemical process.
The main techniques applied to process mineralogy are:

optical microscopy (transmitted and reflected light)

instrumental analysis (XRD, SEM, DTA, TG, IR, XRF, AAS, etc ...)

mass balance (stoichiometric balance)

mineral processing unit operations (particle analysis, magnetic separation, flotation,


gravity concentration, cyanidation, etc...)

selective chemical extraction (diagnostic leaching for gold, sequential extraction of


hydrous ferric oxides, etc.)

laboratory techniques to study mineral properties related to industrial performance


(filtration, brightness, oil adsorption, viscosity, etc.)

Table 1 - Most Used Analytical Methods in Process Mineralogy


To Identify and Sometimes Quantify Minerals
Technique

Principle

Purpose

Polarized Optical
Microscopy

Transmitted or reflected polarized light


interacts with sample (thin or polished
section) revealing optical properties of
minerals.

Identification of minerals and specific


features such as alteration, grain size,
associations, etc. Modal analysis.

X-ray Diffraction
(XRD)

X-ray radiation strikes on a pulverized


sample and diffraction occurs on all
crystallographic planes of the minerals.

Identification of crystalline minerals.


Modal analysis.

Scanning Electron
Microscopy
(SEM)

Electron beams strike on a conductive


sample. Secondary and back-scattered
electrons generate image. Fluorescent xrays can be discriminated by energy
(EDS) or wavelengths (WDS).

Identification of minerals and specific


features. Quantitative microanalysis of
elements in regions (1 m) of minerals.
Modal analysis.

Electron beams pass through a conductive


thin sample (< 0.1 m) and provide image
on a fluorescent screen. Electrons
scattered by atoms of the sample and xrays can be analyzed.

Identification of clays and clayminerals.


Quantitative microanalysis of elements in
mineral regions. Resolution of 1 m.

In TG, mass changes of a minerals are


monitored as a function of temperature.
In DTA, the difference in temperature
between the sample and a reference is
recorded.

Complementary tools for quantitative


determination of minerals (mostly clays).
Useful for amorphous minerals.

Infrared
Spectroscopy
(IRS)

Absorption of IR radiation by minerals as


a function of the atomic weights, lengths,
strengths and interatomic bonds in the
structure of minerals.

Qualitative and quantitative analysis of


minerals (mainly amorphous ones and
clays).

X-ray
Photoelectron
Spectroscopy
(XPS)
and Auger
Spectroscopy

Low energy x-rays strike on the surface


(2 m) of the sample and eject electrons
from the inner shells. These electrons are
analyzed. The atom relaxation process
can eject another electron (Auger) from
outer shells.

Qualitative and quantitative analysis of


elements (all except H and He) at the
mineral surface (chemical bonding,
oxidation state, adsorbed species, etc.)

Transmission
Electron
Microscopy
(TEM)
Thermal Analysis
(Termogravimetry
TG,
Differential
Thermal Analysis DTA)

Table 2 - Most Used Analytical Methods in Process Mineralogy


- Chemical Analysis
Technique
X-ray
Fluorescence
Spectroscopy
(XRF)

Principle

Purpose

X-ray radiation strikes on a pulverized or fused sample


and all elements emit characteristic x-rays that can be
discriminated by their energies (EDS) or wavelengths
(WDS).

Qualitative and
quantitative analysis of
elements with atomic
number between 6 and
92

Atomic Absorption
Spectroscopy
(AAS)

Sample is digested with acids and elements in solution are


converted into atomic vapor by high temperature flame
(1700 C). The atoms selectively absorb light from lamps
emitting specific wavelengths that are characteristic of the
elements of interest. The amount of light absorbed is
proportional to element concentration in the solution.

Sequential analysis of
elements (mostly
cations). For gold
analysis, a fusion
procedure + acid
digestion (fire assay)
precedes the AAS
analysis.

Inductively
Coupled PlasmaAtomic Emission
Spectroscopy
(ICP-AES)

Sample is digested with acids and solution is sprayed into


a Argon plasma torch (10,000 C). The atoms are excited
and decay emitting radiations that are separated by a highresolution monochromator.

Simultaneous analysis of
elements (mostly
cations).

Ultra-violet visible
Spectroscopy

Atoms and molecules in solution absorb UV and visible


light (200 to 1100 m). The wavelength of the absorbed
radiation is a characteristic of the molecule.

The absorption of
characteristic
wavelengths allows
quantifying the
concentration of that
specific molecule in a
solution.

Selective Chemical
Extraction

Reagents selectively dissolve minerals revealing which


metals are associated with them. Usually sequential
extractions are applied to remove metals:

Identify metal-bearing
minerals: exploration
and environmental
purposes. Bioavailability
of heavy metals can be
inferred.

1) weakly adsorbed on clays;


2) strongly adsorbed on hydrous ferric and manganese
oxides;
3) associated with organic matter;
4) in mineral structure.

Atomic Spectroscopy
An element to be analyzed is converted
into a neutral atomic or ionic vapor.
Electromagnetic radiation absorbed or
emitted by electrons during orbital
transitions is the analytical signal of
interest.
Atomic Absorption Spectrometry and
Atomic Emission Spectroscopy (e.g. ICPAES) are examples of atomic spectroscopy
techniques.

Mineralogical Analysis
Qualitative and Quantitative Analysis
There are approximately 3500 known minerals. This number is slowly increasing as new
minerals are discovered by modern analytical methods and new mineralogical environments.
Only 250 to 300 minerals form common commercial products or occur in significant
proportions in ores or mineral deposits. However it is important to know the gangue minerals,
as they can contaminate concentrates or final products as well as cause impact to the
environment.
There are many diagnostic properties usually applied to hand specimens: crystal habits,
cleavage, fracture, hardness, specific gravity, color, streak, luster, etc. Some of these
properties bring more certainty to mineral identification than others.
In process mineralogy, we need to identify and quantify all minerals present in a
representative sample.
The main identification techniques are:

optical microscopy

electron microscopy

x-ray diffraction
Auxiliary methods are also applicable to help identification or to enhance mineral
concentration in the sample:

qualitative and quantitative chemical analysis

sequential or selective chemical extraction

mineral separation (based on certain properties)

The main quantitative analysis techniques (also called modal analysis) are:

mineral separation (each mineral species is weighed separately)

microscopic techniques (point counting and image analysis)

quantitative x-ray diffraction

stoichiometric balance

Mineral Classification
In classical mineralogy, chemical composition and internal structure have been the basis for
the classification of minerals. Dana's Classification, shown in Table 1 below, is widely
accepted.
In process mineralogy, minerals are classified by their uses or functions, as shown in Table 2
below.
Table 4 - Minerals Classified by Use / Functions
Classes
ore minerals
industrial minerals
energy minerals
gemstones
gangue minerals

Use / Function

Examples

metals extraction

CuFeS2

provide properties for materials,


have specific industrial use

kaolin for paper, garnet for


abrasives

power generation

coal

jewelry

diamond

headache for miners

clayminerals

Table 3 - Mineral Classification


Classes
Native Elements
Sulfides
Sulfosalts

Examples
Gold, Au
Pyrite, FeS2
Enargite, Cu3AsS4

Oxides/Hydroxides

Hematite, Fe2O3; Goethite, FeO(OH)

Halides

Fluorite, CaF2

Carbonates

Calcite, CaCO3

Nitrates

Nitratite, NaNO3

Borates

Borax, Na2B4O5(OH)4.8H2O

Phosphates

Apatite, Ca5(PO4)3(F,Cl,OH)

Sulfates
Tungstates
Silicates

Barite, BaSO4
Scheelite, CaWO4
Plagioclase, NaAlSi3O8-CaAl2Si2O8

From the process and environmental perspective, all minerals must be known and their
properties characterized. For instance, knowing the type of gangue-minerals, we can predict
the acid neutralization potential of a tailing.
In this case, we must identify the main mineral factors.

Mineral Factors
Mineral Factors
Mineral factors are important for:

beneficiation (physical and/or physico-chemical processes)

extractive metallurgy (chemical processes)

industrial use (in the case of industrial minerals)

Evaluating a rock fragment for its valuable mineral.

Texture has implications for liberation processes. Intergrown or aggregates of minerals are
difficult to liberate. In many circumstances grains of the valuable mineral are completely
inaccessible to reagents. Gold locked in sulfide particles is a common example. A fractured
texture can also facilitate penetration of cyanide into rock fragments in a heap leaching
operation.
Shape of the grains has influence on gravity concentration methods (gold flakes are difficult
to concentrate on shaking tables) and on liberation and reaction rate. This is important for
industrial minerals, e.g. asbestos, CaCO3, etc.
Grain size of minerals has influence on liberation, reaction rates in hydro and
pyrometallurgical processes, recovery of minerals in beneficiation processes and specification
of products. Kaolin to be used as paper coating must have more than 80% of the grains below
2 m.
Mineral Associations. Preferential association of the minerals of interest is important to
predict contamination of products and the liberation process. Weak boundaries between
mineral and gangue particles favor liberation by "detachment".
Mineral Surface. The surface must be exposed enough and not oxidized to be suitable for
flotation. Sulfide floatability is greatly affected by surface oxidation.
Porosity influences reagent consumption in flotation. A rate of reaction of a particle with a
reagent (liquid or gas) also depends on the rate at which this reagent diffuses to the interior of
the particle through pores and cracks and reacts there. Apatite with large number of pores ( <
0.01 m ) is good material for phosphoric acid manufacturing and for direct use as a fertilizer.
Impurities or inclusions determine the quality of the products. Impurities (as solid solution,
unliberated particles, or particles dragged to concentrates) result in large penalties when
concentrates are sold. Silica as inclusion reduces the price of the Zn concentrates (Cn$ 3.00
for each 1% of SiO2 in excess of 2.5%); each 1% of Fe in solid solution in sphalerite (ZnS)
has penalties of Cn$ 1.80; for each 100 ppm Hg ( > 50 ppm) in 1 short ton of Zn concentrate,
the price is reduced Cn$ 3.00 (Cominco Smelter, 1997).
Physical and chemical properties determine the beneficiation process to be selected and the
performance in industrial processes. Properties vary with the chemical composition of

minerals. Rutile (TiO2) in India is magnetic. Zircon in Nigeria is more magnetic than
ilmenite.
Crystal structure. Reactivity of solids to leaching solutions varies from one polymorph to
another. Calcite is more reactive than aragonite. Defects in the structure associated with shape
and type of crystal structure bring special properties for some minerals. Natural -MnO2,
"nsutite", is adequate for dry batteries and -MnO2, "pyrolusite" is not.
Alteration products have a strong effect on all beneficiation processes as well as increasing
reagent consumption in metallurgical processes. Clay minerals mixed with hydrous ferric
oxides form a thin layer on gold particles that prevents flotation. The presence of hydrous
ferric oxides in oxidized copper ores is one of the main sulfuric acid consumers.

Element Distribution in Screened Fraction


Depending on lithology, minerals tend to have different size distribution. For example, in
placer deposits, ore-minerals tend to have a uniform grain size distribution. In other ores,
valuable minerals do not show concentration in a specific size, i.e. they are distributed all
over the screened fractions.
A high concentration of the valuable mineral in coarse fractions does not give any indication
about its liberation. In other words, if chemical analysis shows that there is a concentration of
a certain element (consequently mineral) in a coarse fraction, this does not mean that the
valuable mineral is coarse and free.
But when the particle distribution shows the presence of a valuable element (mineral) in fine
fractions, this means that the mineral is fine, but it is NOT necessarily liberated.
Table 1 - Size and tungsten (W) distribution of a pegmatite sample
Total of highlighted rows - 88% W, 41% ore mass

Sieve size
(mesh)

Weight retained
(%)

W
(%)

DW
(%)

+6

4.31

0.61

1.79

-6 +8

2.65

0.20

0.36

-8 +10

5.78

2.09

8.22

-10 +14

4.32

3.45

10.1

-14 +20

5.75

4.01

15.7

-20 +28

7.84

4.12

22.0

-28 +35

8.23

2.93

16.4

-35 +48

8.94

2.54

15.4

-48 +65

6.02

0.81

3.32

-65 +100

6.21

0.60

2.53

-100 +150

7.55

0.21

1.08

-150 +200

8.32

0.22

1.25

-200 +270

8.97

0.12

0.73

-270 +400

7.30

0.13

0.65

-400

7.81

0.080

0.43

Total (calculated)

100

1.47

100

Total (analyzed)

1.36

For example, Table 1, above right, shows the particle size and tungsten (W) distribution of a
representative sample of a pegmatite , containing wolframite , crushed below 4 mesh
(4.74 mm).
Clearly, in this ore, wolframite has a tendency to be concentrated in the coarse fraction, but
this does not mean that this mineral is liberated. Classification can eliminate 60% of mass and
concentrate 88% of wolframite.
For example, Au distribution in this ore follows the mass distribution, shown in Figure 2
below. This give us a hint that Au is likely very fine.

Correlation between Cu and Au is a good indication that bulk concentrate of copper minerals
can take gold together, shown in Figure 3 below.

Figure 3. Correlation between Cu and Au is a good indication that bulk concentrate of copper
minerals can take gold together.
For example, Au distribution in Figure 4 below shows some correlation with Ag distribution.
Cu in Figure 5 below shows poor correlation with S due to the presence of different copper
minerals, such as tennantite (Cu,Fe)12As4S13 and mooihoekite Cu9Fe9S16 as well as other
non-copper sulfides such as galena PbS and pyrite FeS2.
Figure 4

Au distribution shows some correlation with Ag distribution.

Figure 5

Cu shows poor correlation with S due to the presence of different copper minerals.

Part 2 - Optical Microscopy


Analysis by Transmitted Light
Visible Light
Visible or white light is an electromagnetic wave with a series of wavelengths between 390
(purple) and 770 m (red), shown in Figure 1 below. Monochromatic light consists of a single
wavelength within this range.
The electromagnetic fields associated with light waves are directed at right angles to the
direction of travel of the beam. If white or monochromatic light passes through a special
polarizing filter, then the light becomes plane-polarized, i.e. the electromagnetic field is
constrained to vibrate in one direction only and this direction is still at right angles to the
direction of travel of the beam.
Figure 1

Visible or white light is an electromagnetic wave.

Polarizing Optical Microscope (transmitted light)


A polarizing optical microscope (transmitted light), shown in Figure 2 below, contains:

a lens, which is usually 10X

polarizing film which can be either slid or flipped into the light path. The vibration
direction is set at 90 to the lower polarizer.

a primary magnification system. The lenses permit changes in magnification; usually


2.5X or 3.2X, 10X, and 40X.

a rotating plate, where the thin section is placed

a polarizer, which converts non-polarized light from source into plane polarized light

a light source
Figure 2

Figure 2. Polarizing Optical Microscope (transmitted light).

Refraction
In isotropic substances, such as glass, liquids or crystals that belong to the isometric crystal
system, light moves in all directions with equal velocity and hence each isotropic substance
has a single refractive index, shown in Figure 3 below.
In anisotropic substances, light is broken into two polarized rays vibrating in perpendicular
planes, shown in Figure 4, below.

Figure 3. In isotropic substances light moves in all directions with equal velocity.

Figure 4. Light is broken into two polarized rays.

In hexagonal and tetragonal (anisotropic) crystals there is only one direction in which
ordinary light moves in the same direction as extraordinary light. This is called the optic axis,
which coincides with the c axis (see Figures 6 and 7 below). These crystals are called
uniaxial. Orthorhombic , monoclinic and triclinic crystals have two optical axes and
they are optically classified as biaxial.

Uniaxial Crystals
Uniaxial crystals, shown in Figure 5 right, are divided into two optical groups: positive and
negative.

Positive: when the O ray has greater velocity than the E ray.

Negative: when the E ray has greater velocity than the O ray.

Figure 5. Uniaxial crystals. A. The uniaxial indicatrix is a geometrical figure that is helpful
in visualizing the relation of the refractive indices and their vibration directions. B. Cross
sections of uniaxial indicatrix. (From: Wahlstrom (1951))
There are many refractive indices in uniaxial crystals, depending on direction. Usually just
the two principal indices are represented and the difference between them is called
birefringence . This is better observed with crossed polars.

Some anisotropic minerals absorb more light (some wavelengths) in one vibration direction
than in the other. This phenomenon is called pleochroism . Examples are tourmaline ,
biotite , and hypersthene .