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Fundamentals of Fire Assay

Presentation · August 2018

DOI: 10.13140/RG.2.2.22438.78408

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FIRE ASSAY FUNDAMENTALS
Dr. Corby G. Anderson
Harrison Western Professor
Metallurgical and Materials Engineering
Room 270 Hill Hall
Colorado School of Mines
E: cganders@mines.edu
T: 303-273-3580
 INTRODUCTION
The beginnings of fire assaying can be
traced to the finds in Troy II (about 2600
B.C.) and in the Cappadocian Tablets
(2250 -1950 B.C.). These finds prove that
very pure silver was made in the twenty-
fifth century B.C. From this evidence we
must conclude that the cupellation
process, and therefore fire assaying, was
invented in Asia Minor in the first half of
the third millennium B.C. shortly after the
discovery of the manufacture of lead from
galena (Forbes, 1950).
 INTRODUCTION
The first convincing evidence of the
production of silver from lead ores is
the cupel buttons found at
Mahmatlar in the late third millenium
B.C. and that are now in the Hittite
Museum in Ankara, Turkey. Biblical
references to the use of fire-assay
techniques can be traced to the
prophet Moses (about 1300 B.C.)
 INTRODUCTION
"The promises of Yahweh (God) are
promises unalloyed, silver purged in
a crucible, of clay refined seven
times."

“ The fining pot [cupel] is for silver

and the furnace for gold: but the
Lord trieth the hearts."
 INTRODUCTION
"From Jeremiah
"The bellows blow fiercely, but the lead
comes whole from the fire. It's useless to
go on refining, the wicked are not
removed."

Zechariah states:
“ And I will bring the third part through the
fire, and will refine them as silver is
refined, and will try them as gold is tried:
 INTRODUCTION
More reference is made to the "fining
pot" (cupel) in Malachi;
"And he shall sit as a refiner and
purifier of silver: and he shall purify
the sons of Levi, and purge them as
gold and silver, that they may offer
unto the Lord an offering in
righteousness."
 INTRODUCTION
These references are but a few that
demonstrate the extent to which fire-
assay techniques permeated Asia Minor
in ancient times. The Romans were able
to desilver lead down to 0.01 percent or
even to 0.002 percent in some cases
and marked their cupelled desilvered
lead "EX ARG." Roman lead pipe was
found to be desilvered almost
completely. In addition to the
employment of fire-assay techniques
for refining lead and silver, the Romans
were the first to make extensive use of
the amalgamation process.
 INTRODUCTION
With the fall of the Roman Empire by the
invasions and conquests of the barbarian
hordes, intellectual life stagnated for about
500 years. With the revival of learning in the
latter centuries of the Middle Ages, the art of
fire assaying was renewed vigorously. One
man stands out above all in this period -
Agricola (1494-1555). In about 1529 he began
to write "De Re Metallica" (1556), which he
completed in 1550 but did not send to the
publishers until 1553. Preparation of the
woodcuts delayed publication until a year after
the death of Agricola.
 De Re Metallica
Written in 1556 by Agricola

Georgius Agricola (24 March 1494 – 21 November 1555) was a German

scholar and scientist. Known as "the father of mineralogy", he was born
at Glauchau in Saxony. His real name was Georg Pawer; Agricola is the
Latinised version of his name, Pawer/(Bauer) meaning farmer. He is best
known for his book De Re Metallica.
 De Re Metallica
Written in 1556 by Agricola
Woodcuts
 De Re Metallica
Written in 1556 by Agricola
Woodcuts
 INTRODUCTION
 In summation, the use of lead oxide
for the fire assay process dates back
to the finds in Troy II and the
Cappadocian Tablets about 3000
B.C.
 Now used for Au, Ag, and PGM’s

 Historically used for Pb, Cu, Bi, Sn,

Sb, Hg and Fe.
 FIRE ASSAY AUTHORS
 “De La Pirotechnia”, 1540 Vannoccio
Biringuccio
 “De Re Metallica”, 1556 Georgius
Agricola
 “Treatise on Ores and Assaying”,
1574 Lazarus Ercker
 MODERN FIRE ASSAY
AUTHORS
 ‘The Metallurgy of Gold’, 1906, T.K. Rose
 A Manual of Practical Assaying’, 1908,
Furman and Pardoe
 ‘Modern Assaying’, 1910, J.R Smith

 ‘A Textbook of Assaying’, 1910, C. and J.

Beringer
 “Textbook of Fire Assaying’, 1915, E.E.
Bugbee
 MODERN FIRE ASSAY
AUTHORS
 ‘A Manual of Fire Assaying’, 1929, C. H.
Fulton
 ‘Fire Assaying’, 1940, O. Shepard and
W.Dietrich
 The Sampling and Assay of the Precious
Metals, 1947, E.A.Smith
 Assay and Analytical Practice in the South
African Mining Industry, 1986, W. Lenahan
and R. Murray-Smith
 De Re Metallica
Written in 1556 by Agricola
“It is necessary that the assayer who
is testing ore or metals should be
prepared and instructed in all things
necessary in assaying, and that he
should close the doors of the room in
which the assay furnace stands, lest
anyone coming at an inopportune
moment might disturb his thoughts
when they are intent on work.”
 FIRE ASSAY ANALOGY
 Pyrometallurgical lead smelting.
 Controlled or incomplete reduction.
 FIRE ASSAY ANALOGY
 Pyrometallurgical solvent extraction.
 Utilizes ‘selective extractant’ for Au,
Ag or PGM’s.
 Requires proper ‘diluent’ slag.

 The ‘selective extractant’ is

‘strippable’ producing a pure,
concentrated precious metal.
 GENERAL FIRE ASSAY
METHODOLOGY
 Accurate and representative, well
characterized sample.
 Determine reducing or oxidizing
power of material.
 Appropriate precious metals
collector.
 Correct slag and fusion formulation.

 Correct lab skills.

 DISCUSSION
OF SAMPLING
 A key to a successful fire assay.
 Particulate sampling paper on Blackboard.
 Three key aspects of particulate sampling;
– 1). Each particle must have an equal
opportunity to be sampled.
– 2). The correct amount of representative
sample related to the top size of the particle
distribution must be taken.
– 3). Take as many sub samples as reasonable
to create the correct amount of required
representative sample.
FUNDAMENTAL ASSAY UNITS
 An assay ton (AT) is 29.166 grams.
 There are 14.583 Troy ounces of
precious metals in one pound.
 In the USA Precious Metals content is
expressed in Troy Ounces per Short
Ton. A short ton is 200 lbs.
 One troy ounce is 31.1035 grams.

 A metric tonne is 2204.62 lbs.

 So, 34.2857 grams per tonne is one

Troy Ounce.
 FUNDAMENTAL CHEMISTRY
OF FIRE ASSAY

Fusion
12PbO + C6H10O5  12Pb + 6CO2 +5H2O
162 2,48
Cupellation
Pb + ½ O2 PbO
ESSENTIAL REAGENTS USED
IN FIRE ASSAYING
 Basic Reagents
Litharge – PbO
Sodium Carbonate – Na2CO3
 Neutral Reagents
Fluorspar – CaF2
Cryolite – AlNa2F6
 Acid Reagents
Silica, quartz, glass – SiO2
ESSENTIAL REAGENTS USED
IN FIRE ASAYING
 Acid Reagents
Borax – NaB4O7:10H2O
Borax Glass - NaB4O7
 Reducing Reagents
Flour, carbon,metallic iron
 Oxidizing Reagents
Niter – potassium nitrate – KNO3
Litharge – PbO
 BASIC OPERATIONS OF
FIRE ASSAY
 Sampling, weighing and combining the
material to be assayed with an
appropriate flux.
 Fusing the mixture in the crucible.
 Pouring the reduced button.
 Separating slag from button.
 Cupeling the button.
 Parting the bead.
 Scorification if necessary.
FIRE ASSAY REDUCING
POWER TEST
 FUNDAMENTAL CHEMISTRY
OF FIRE ASSAY

Fusion
12PbO + C6H10O5  12Pb + 6CO2 +5H2O
162 2,486
Cupellation
Pb + ½ O2 PbO
REDUCING AND OXIDIZING POWER
FLUX AND SLAG CHARACTERISTICS
EXAMPLE FLUX MIXTURES.
EXAMPLE FLUX MIXTURES.
EXAMPLE FLUX MIXTURES.
CRUCIBLE FUSION
CRUCIBLE FUSION
CRUCIBLE FUSION
CRUCIBLE FUSION
CRUCIBLE FUSION
FIRE ASSAY MOLDS AND TRAYS
CRUCIBLE FUSION
CRUCIBLE FUSION
CRUCIBLE FUSION
CRUCIBLE FUSION
 Pb BUTTONS
The lead button is separated from the
slag using a hammer. It can then be
pounded into a cube to be placed in a
cupel
Pb BUTTONS
 FLUXES AND SLAGS
 Slag components classified according
to acidity or basicity.
 Classified according to the silicate
degree which is the ratio of oxygen
in the acids to oxygen in the bases.
 Metal oxides tend to be soluble in
metallurgical slags.
FLUXES AND SLAGS
 ASSAY SLAG COLORS
 Green slags indicate ferrous silicates
or copper.
 Brick red slags indicate copper and
the absence of iron. Color from
cuprous silicate or cuprous borate.
 White to gray white (opaque) slags
indicate calcium, magnesium,
aluminum or zinc.
 ASSAY SLAG COLORS
 Antimony gives a greenish-yellow
color.
 Iron bearing slags are yellow-brown
or black. An acid slag bearing iron
will be pale green and transparent.
ASSAY SLAG COLORS
 ASSAY SLAG COLORS
 Cobalt blue slags indicate cobalt.
 Purple to light pink slags indicate
manganese.
 Slags should always be examined for
‘shotting’ of entrained particles of
lead.
 IMPURITIES IN THE SLAG
 Shotting – metals entrained in slag.
Modify slag viscosity.
 Speiss - As, Sb - Heavier than matte
but lighter than lead. Usually only
found when copper present. Use
more litharge.
 Matte - iron and copper sulfides.
 IMPURITIES IN THE LEAD
BUTTON
 Most base metal impurities cause
problems in cupellation.
 Bismuth is special case.

 Electomotive series shows that

besides PM’s only Sb, Bi, As, Cu,Te,
and Hg are below Pb. Thus, they
may be reduced with Pb.
IMPURITIES IN THE LEAD
BUTTON
 IMPURITIES OF THE LEAD
BUTTON
 Bismuth – acts like lead – bead
‘sweating’.
 Antimony, Arsenic, Telleriurm and
Copper – easy to oxidize with excess
litharge.
 When in doubt use excess litharge.

 Scorification used at times.

IMPURITIES IN THE LEAD
BUTTON
IMPURITIES IN THE LEAD
BUTTON
 CUPELLATION
 Oxidizing the lead button from fusion
back to litharge.
Pb + ½ O2  PbO
 Cupel, either magnesia or ‘bone ash’
absorbs litharge and base metals.
 Precious metals are left in a dore
‘bead’.
 CUPELLATION

 Heat furnace to 850O C.

 Place cupels in furnace with
‘deadheads’ for 15 minutes to
850O C.
 Hammer lead buttons into cubes.

 Place button in cupel.

 When cupel button ‘opens’ lower

temperature.
 CUPELLATION

 When lead is nearly gone, raise

temperature up to ‘drive’ the lead
out.
 Be careful with high silver buttons
because of ‘spitting’.
 Take cupels from furnace and
remove precious metal ‘beads’.
CUPELLATION
CUPELLATION
CUPELLATION
CUPELLATION
CUPELLATION
CUPELLATION
Feathering
CUPELLATION
 THE BEAD SILVER PARTING
PROCESS
 Used to separate silver from gold in
final bead.
 Must have 3 to 1 ratio of silver to
gold. ‘Inquartation’ with silver used
to ensure this ratio.
 Use 1 part nitric acid and 7 parts
water.
 Heat bead in nitric solution.
FIRE ASSAY TOOLS
FIRE ASSAY TOOLS
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FIRE ASSAY FUNDAMENTALS

Dr. Corby G. Anderson
Harrison Western Professor
Metallurgical and Materials Engineering
Room 270 Hill Hall
Colorado School of Mines
E: cganders@mines.edu
T: 303-273-3580