The Metallurgy of Some Carat Gold

Jewellery Alloys
PART I — COLOURED GOLD ALLOYS

Allen S. McDonald and George H. Sistare

Handy & Harman, Fairfield, Connecticut, U.S.A.

The classification of gold alloys in terms of caratage and colour provides

no guidance as to the properties and working characteristics of the many
carat gold alloys used in jewellery fabrication. Logical relationships do
exist, however, between the composition, metallurgical structure and
properties of such alloys, and these emerge from a study of the phase
diagrams of the alloy systems involved. Part I of this review deals with
coloured gold alloys. Part II will discuss their nickel containing counter-
parts and will appear in the next issue of Gold Bulletin.

Most carat gold for jewellery falls into one or other Three quasi-binary vertical sections of the ternary
of two major categories, the coloured gold alloys diagram at constant gold contents characteristic of
based on the gold-silver-copper or the gold-silver- jewellery alloys (10, 14 and 18 carat) are schematical-
copper-zinc system and the white gold alloys. ly represented in Figure 4 where the parameter used
Although many coloured gold alloys contain zinc on the abscissa is defined as:
(from less than 1 to about 15 weight per cent), it is
valid to introduce this group in terms of the gold- Ag wt.%
Ag' = x 100 (per cent)
silver-copper ternary system, from which all of the Ag wt.°Io + Cu wt.%
alloys inherit certain fundamental metallurgical
characteristics. After establishing these, the effects of Gold-silver-copper and gold-silver-copper-zinc-
zinc will be introduced, and it will then be seen that alloys can be logically classified and discussed in
in the amounts used this element does not change terms of two parameters, namely the caratage or gold
these characteristics in kind but rather interacts to content and Ag'.
modify them in a regular and symmetrical way. Given constant gold content sections of the ternary
Figure I presents the gold-copper, copper-silver diagram, for example the 14 carat section in Figure 4,
and silver-gold binary phase diagrams (1). The ter- the concept of three `types' of alloy based on the im-
nary phase diagram can be established by progressive- miscibility gap and defined by values of Ag' can be
ly adding gold to the copper-silver system. One might introduced.
expect a liquidus valley to extend from the copper- Type I where Ag' ranges from 0 to about 10 per
silver eutectic point at 780°C to the gold-copper cent or from about 90 to 100 per cent. These alloys
liquidus minimum at 911°C. This valley exists and is exist primarily as homogeneous solid solutions at all
shown in Figure 2. One might also expect the solid temperatures below the melting point. Alloys of this
state immiscibility field in the copper-silver system to type are soft in the annealed condition and are not
intrude into the ternary diagram to a considerable ex- age-hardenable.
tent. Indeed it does, shrinking laterally and vertically, Type II where Ag' is in the range from about 10 to
as compositions approach the gold corner. This is 25 per cent or 75 to 90 per cent. These alloys will
illustrated in Figure 3, where the solid state isother- exist as homogeneous solid solutions at temperatures
mal boundaries of the immiscibility field have been
projected onto the room temperature plane. The ex-
istence of this immiscibility field is by far the most
equilibrium at room temperature (Ag Au) will _.0 „ _
above the immiscibility gap, but if slowly cooled to

precipitate in copper-rich alloys and cc (c „_ A ) in silver-

important factor in determining the basic rich alloys. Type II alloys are moderately soft in the
metallurgical characteristics of the coloured jewellery annealed condition but are age-hardenable by heat
gold alloys. treatment.

r7.7
 GOLD-COPPER COPPER-SILVER
GOLD ATOMIC PER CENT °C COPPER ATOMIC PER CENT
°C 9080 70 60 50 40 30 20 10 90 80 70 60 50 40 30 20 10

TI1LLI
1100 1100
1084° WOO
1064 °
1050 1000
962°
LIQUID LIQUID
1000 900
(Cu)
950 800 780°

900 911°,80.1°4
SOLID SOLUTION
a(AuCu) 700
1 921
281 88 (Ag)

IMMISCIBILITY

EH'
a (Cu)` a (Ag)
450 600
410 °,75.6%
400 390 °, 50.8°I 500

350 r - 4 00
Cu 90 80 70 60 50 40 30 20 10 Ag
AuCu3 X ^ COPPER WEIGHT PER CENT
AuCu
300

SILVER-GOLD
250
240 ° ii ° SILVER ATOMIC PER CENT
jI^ (
90 80 70 60 50 40 30 20 10
200 10 70
Au 90 80 70 60 50 40 30 20 10 Cu ' 1064
GOLD WEIGHT PER CENT
1050

Fig. 1 Gold-copper, copper-silver and silver-gold 1030 _..._.- -- — LIQUID ---- --- 'r -- -- --_..-
binary phase diagrams. On the gold-copper diagram, i
note the minimum liquidus temperature and the ex- 1010
istence of two ordered phases, AuCu and AuCu 3 . The
SOLID SOLUTION
copper-silver diagram shows that due to the eutectic
990 a (Ag,Au)
decomposition of the homogeneous liquid phase into

TIILt
copper-rich and silver-rich phases, binary alloys are
970
two-phase in the solid state except when either of cop-
per or silver is present in a very small quantity only. 962 °
950
Silver-gold binary alloys are single phase at all concen- Ag 90 80 70 60 50 40 30 20 10 Au
trations. After (1) SILVER WEIGHT PER CENT

Au Au

10 -- 90

010
20 80
889 ° °
/30 --- 70
°
40 60

ci
50 -- 843 ° 50 -

/60 40

80

Cu 10 20 30 40 50 60 70\ 80 90 Ag Cu 10 20 30 40 50 60 70 80 90 Ag
SILVER WEIGHT PER CENT SILVER WEIGHT PER CENT

Fig. 2 Projection on the room temperature plane of the Fig. 3 Projection on the room temperature plane of the
gold-silver-copper ternary phase diagram of some gold-silver- copper ternary phase diagram of some
isotherms on the liquidus surface. A liquidus valley ex- is6thermal solid state boundaries of the immiscibility
tends frone the silvel`edpper eutectic point to the gold- field. After 11)
copper liquidus minimum. After (1)

67
 IS CARAT 14 CARAT 10 CARAT

Ag, Wt. °/° Ag,Wt, % Ag, Wt. %

0 10 20 0 10 20 30 40 0 10 20 30 40 50
1100

1000 OJ5
v^OJ\
900
SOLI DU S SOLID \
0LUTION
600 DUS
a(Au,Ag,Cu

700 SOLID SOLUTION SOLID SOLUTION

W a(Au,Ag,Cu) a (Au,AgCu)
a IMMISCIBILITY
600
a (Cu-Au)'(Ag-Au)
Ui
a
500
Ui
I- IMMISCIBILITY
400 a(Cu-Au)`a(Ag-Au)

300
' (IMMISCI-
BILITY
200 AuCu^ a(Cu-Au)
(Ag-Au)
‚vu -
80 100
0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60

Ag' 'I, Ag %° Ag', °%

Fig. 4 Schematic quasi-binary sections at constant caratage of the gold-silver-copper ternary phase diagram. The
parameter Ag' is defined in the text

Au
RY_REDYELLOW copper alloys could be expected to range from
10 Q 90 DY-GREEN
YELLOW
`copper-red' near the copper-rich corner, to 'gold-
20
18Ct. o
80 yellow' near the gold-rich corner, to `silver-white'
30 > 0V 70 near the silver-rich corner. A more precise delinea-
e46
40
i tion (2) of the actual colour fields is illustrated in
14Ct. 60
= x cti^ Figure 5.
3 3 50 .p^
It will be noted in Figure 5 that `copper-red'
_ 1 oct. — J W°— 40 dominates not only the copper-rich corner but most of
W
70RED
/ 30
the copper- and gold-rich side of the diagram. Alloys
in these red and reddish areas can be, and are, made
uj, 20
yellowish by an addition of zinc.
W WHITISH
90 10 The effect of zinc on the concept of alloy types as
defined above, will be understood if it is borne in
Cu 10 20 30 40 50 60 70 80 90 Ag mind that the addition of this element tends to reduce
SILVER WEIGHT PER CENT (3) the volume of solid state immiscibility in the ter-
Fig. 5 Relationship between the colour and com- nary phase diagram.
position of gold-silver-copper alloys. After (2) The small amounts of zinc (about 0.5 per cent or
less) added as a deoxidizer in 10 and 14 carat alloys
have no significant effect on the metallurgical
Type III where Ag' is in the range from about 25 to characteristics under discussion. Larger additions (up
75 per cent. These alloys are homogeneous solid solu- to about 15 weight per cent) are, however, used to
tions at temperatures above the immiscibility gap, but change the red colour of low and middle caratage
if slowly cooled to equilibrium at room temperature copper-rich alloys to reddish yellow or dark yellow.
they decompose into both '(Ag-Au) and -C( Cu.Au) . Alloys These soften the alloys in both the annealed and
of this type are hard in the annealed condition. They precipitation hardened state. This is a consequence of
harden markedly during air cooling and are difficult the narrowing and reduction in height of the two
to quench. Type III alloys are age-hardenable. phase area on each of the constant gold content sec-
In the jewellery industry, alloys are usually tions of the ternary diagram shown in Figure 4.
classified in terms of caratage and colour rather than These general concepts will aid a survey of some
of metallurgical properties. The hue of gold-silver- commercial alloys. For this purpose, the reader will

68
find it useful to imagine the metallurgical concept of ing schedule best suited to each particular alloy. For
alloy types as a grid that may be superimposed on the example, annealing at 650°C is sufficient to both
colour diagram of Figure 5. Thus the jeweller's recrystallise and homogenize all of the alloys under
classification of alloys based on caratage and colour discussion. In practice, however, with wrought
can be translated into the present metallurgical material, one needs to steer clear of both the Scylla
classification based on caratage and Ag' values. and Charybdis of gold jewellery annealing for subse-
quent forming — the directionality of properties
14 Carat Coloured Alloys
associated with under-annealing, and the orange peel
A survey of commercial gold alloys will best begin effects associated with over-annealing. On the other
with alloys of intermediate caratage because at 14 hand, when solution annealing castings for subse-
carat useful alloys can be made at all values of Ag'. quent precipitation hardening where the only objec-
On the 14 carat section in Figure 4, although the im- tive is to put the alloy into solid solution, one leans in
miscibility gap is well developed, there is a substan- the direction of relatively higher temperatures and
tial homogeneity temperature range between the top longer times. In general, the annealing temperature
of the gap and the solidus. This permits alloys at all recommended for shop practice varies with Ag', be-
values of Ag' to be homogenised at elevated ing lowest for type I alloys, intermediate for type II,
temperature and to be quenched as homogeneous and highest for type III.
solid solutions at room temperature. In this quenched The hardness values reported in Table II for an-
or solid solution condition, the hardness varies with nealed samples cover the range that can be expected
Ag', being lowest for type I alloys, increasing rapidly in practice depending on whether or not the alloy is
throughout the Ag' range of type II alloys, and is high adequately quenched. The lower value in the range
in type III alloys. Silver-rich type I and II alloys are can be attained if the alloy is quenched in water. The
somewhat softer than copper-rich type I and II alloys. higher value may result if the alloy is cooled in air.
Workability is essentially related to the hardness The range of hardness values for type III alloys vivid-
range. Type I alloys are the most easily worked. ly illustrates the necessity of fast quenching when
However, they are not hardenable except by cold- these alloys are process annealed for subsequent
working. Type II alloys are more versatile. They are working.
workable in the annealed state and can be precipita- The hardness values after heat treatment reported
tion hardened after fabrication. In special cases where in Table II were determined on samples solution an-
maximum hardness is required (gold pen nibs for in- nealed at 650°C for 30 minutes and water quenched
stance), type III alloys are available. These alloys are prior to hardening at the indicated temperature for 2
complex to process. They are the hardest and most to 4 hours.
difficult to work. They require careful quenching, The hardness values after annealing and water
and if not quenched rapidly and effectively, decom- quenching and the maximum hardness values after
position and resulting hardening will occur. heat treatment which are listed in Table II have been
Examples of 14 carat alloy compositions are given plotted against Ag' in Figure 6. A comparison of this
in Table I. Most of the compositions discussed here plot with the 14 carat section in Figure 4, shows how
are commercial alloys that have been, or are currently well the concept of Ag' imposes order on 14 carat
popular in North America. The particular composi- jewellery gold alloys. The relationship between com-
tions used in various parts of the world depend to a position, hardening characteristics, and the phase
large extent on local hall-marking laws and colour structure of the alloy system is quite symmetrical.
preferences. Proprietary names have been avoided The relationship is further illustrated in Figure 7,
and the alloys in Table I are designated by code which shows the metallographic structures of the
numbers and arranged in order of increasing Ag' and series of alloys coded 110 to 840 (see Table I). These
zinc content. These two factors together with caratage structures were developed by annealing at 650°C for
largely specify the metallurgical nature of each alloy. 1 hour and slow overnight cooling in the furnace.
Table II lists Rockwell superficial hardness values Water quenched samples of the same alloys all had
(HR45T) in the annealed and heat treated conditions. homogeneous solid solution structures. The varying
The values were determined on wrought samples amount of precipitation and decomposition which can
63 x 13 mm, deformed 50 per cent by cold-rolling to take place as compositions shift across the im-
0.8 mm gauge. All samples were annealed at 650°C miscibility field from the copper side to the silver side
for 30 minutes. This treatment led to standard with increasing Ag' is clearly evident.
reference conditions for all the alloys, from which Comparing the hardness values of alloy 110 (11 per
comparative hardenability studies were undertaken. cent Ag', 0.2 per cent zinc) in the quenched and the
It should be emphasized at this stage that in shop hardened conditions with those of alloy 116 (11 per
production, it is usually necessary to select the anneal- cent Ag', 6.4 per cent zinc) and the values of alloy 220

69
 Table
Compositon of Some 14 Carat Gold Alloys Commonly Used for Jewellery Manufacture in North America

Alloy Composition, wt.. per cent Ag' Alloy

code Au Ag Cu Zn per cent type

110 58.3 4.6 36.9 0.2 11

220 58.3 9.1 32.4 0.2 22 II
310 58.3 12.9 28.6 0.2 31 III
400 58.3 16.5 25.0 0.2 40 111
600 58.3 24.8 16.8 0.2 60 III
750 58.3 31.0 10.5 0.2 75 III
780 58.3 32.5 9.0 0.2 78 II
850 58.3 35.0 6.5 0.2 84 II

116 58.3 4.0 31.3 6.4 11 1

224 58.3 8.3 29.2 4.1 22 II

Table 11
Rockwell Superficial Hardness (HR45T) of Some 14 Carat Coloured Gold Alloys in the as Annealed and
Precipitation Hardened Conditions

Alloy Annealed Hardened condition after annealing and quenching

condition HR45T

Hardening temperature

code I HR45T I 205°C 260°C 315°C

110 38-40 42-48 45-46 42-43
220 47-51 68-69 75-76 75-76
310 53-63 73-74 75-76 75-76
400 58-71 70-74 71-73 74-75
600 58-69 70-71 71-72 74-75
750 49-68 68-69 71-72
790 43-53 65-66 68-69
850 34-38 60-62 64-65

116 25-28 32-33 27-28 33-36

224 40-43 65-67 71-72 60-61

Specimens: 50 x 13 x 0.8 mm, cold rolled 50 per cent prior to annealing. Annealing time and temperature: 30 minutes at 650°C. Hardening
time: 2 to 4 hours

220 10 _^- - ^\
(22 per cent Ag', 0.2 per cent zinc) with those of alloy
224
70
HEAT TREATED
224 (22 per cent Ag', 4.2 per cent zinc) in Table II
r Aso and Figure 6, illustrates the softening effect of zinc
! 85
a) additions which was previously referred to.
z 60
10 Carat Coloured Alloys
J
ANNEALED
! 10 AND A comparison of the 10 and 14 carat sections in
50 / QUENCHED \^ Figure 4 shows a broader and higher immiscibility
7.1
110 field at 10 carat. A 14 carat alloy with a particular
/ so value of Ag' can be converted into its `associate' 10
3 40
110 carat alloy by reducing the gold content while main-
0
116 ` taining the same relative proportion of other alloying
e^ 5
elements and thus maintaining the same value of Ag'.
30 -

116 Fig. 6 Rockwell superficial hardness (HR45T l of 14 carat

commercial gold alloys in the annealed and quenched and
20
the heat treated conditions as a function of Ag' ,The alloys
0 20 40 60 80 100
are coded as in Tables I and II
Ag PER CENT

70


\L mm.
I \
Al Alloy 110, Ag' 11%, type I l3 Alloy 220, Ag' _ 22%, type II

.y 310, Ag' = 31%, type III

Cl 4Uo 1l' Alloy 400, Ag' = 40%, type III

r s

#I( `Ld

f
_..., .F
, i t

E) Alloy 6y00, Ag' 60%, type III Fb Alloy 754, Ag' = 75%4, type 111

o i< a

GM Alloy 780, Ag' ° 78%, type II HI Alloy 850, Ag" = 84%, type Il
Fig. 7 Equilibrium microstructures.tleyeloped in 14 carat alloys 110 to 850 (see Table 11 by annealing at 650°C for 1 hour
and slow overnight cooling.
A: Hornvgeneous copper-rich solid solution
B. Homogeneous copperrich solid solution: with silver-rich second phase precipitates at the grain houtndarles
C and D Immiscible copper-rich and silver-rich phases
E to H: Homogeneous silver-rich solid solution with copper-rich second phase precipitates at the grain boundaries

71
Under these conditions, an alloy of a given type been arrived at as described above. The type I alloys
(in the sense defined earlier) at 14 carat will generally (14 carat 116 and 10 carat 119) have mechanical pro-
convert to an alloy of the same type at 10 carat. perties so nearly the same at both caratages that they
However, in some cases the properties of an alloy con- can be processed in essentially the same way. The
verted from 14 to 10 carat may be significantly type II yellow alloys (14 carat 224 and 10 carat 226)
altered, depending on the particular value of Ag'. It show significant differences between the two
can be seen how this takes place by considering caratages. For example, 224 is solution annealed in 30
Figure 3 and imagining lines dropped from the gold minutes at 650°C whereas 30 minutes at 705°C are
corner to particular values of Ag' on the silver-copper required with 226. The optimum precipitation
base. All `associated' alloy compositions falling on a hardening schedule for 224 is ageing between 230 and
particular line have the same value of Ag'. If such a 260°C for 2 to 4 hours, while 226 is aged at 315°C
line falls outside the immiscibility field at 14 and 10 for 1 hour. Heat treatment of the 14 carat alloy at
carat, the properties of the associated alloys will be 315°C will result in overageing and softening while if
very similar at both caratages. They will be relatively the 10 carat alloy is treated at 260°C maximum hard-
soft homogeneous solid solutions and not precipita- ness will not be obtained.
tion hardenable. This is the case for type I alloys. If The maximum hardness of the two alloys after heat
the constant Ag' line falls inside the immiscibility treatment is about 71 HR45T for 224 and 73 HR45T
field at both caratages, it is always the case that it is for 226. These differences are due primarily to the
farther inside the field at 10 carat than at 14 carat relative displacement of the solid solution boundary
because the immiscibility field is broader at 10 carat from the Ag' = 22 per cent line to the left in conver-
than at 14 carat. How this effects changes in proper- ting from 14 to 10 carat. However, alloy 224 which
ties depends on the range of Ag'. Type III alloys, contains 4 per cent zinc converts into 226 with 6 per
which are well inside the immiscibility field at both cent zinc. The additional 2 per cent of zinc at 10 carat
caratages tend to have similar properties at 10 and 14 shifts the solid solution boundary back to the right
carat. However, at 10 carat they are much harder and and therefore reduces the net displacements. The
much more difficult to anneal and quench than at 14 type II green alloys (14 carat 850 and 10 carat 840)
carat. Marked differences can occur in the conversion also exhibit some interesting differences in proper-
of type II alloys. In this range, a yellowish alloy or a ties. Again, the 14 carat alloy can be solution anneal-
greenish alloy `just inside' the immiscibility field at ed at 650°C for 30 minutes, but with the 10 carat
14 carat and capable of only moderate precipitation alloy 705°C for 30 minutes is required. Both can be
hardening may, on conversion to 10 carat be `well in- precipitation hardened at 315°C — 850 in 2 hours
side' the field and precipitation harden to a significant and 840 in 2 to 4 hours. The maximum hardness of
degree. Such displacements relative to the im- the 14 carat alloy in the heat treated condition is 65
miscibility field will also affect the process annealing, HR45T, while it is 70 HR45T for the 10 carat alloy.
solution annealing and optimum precipitation The latter is so much further into the two phase
hardening temperature, optimum ageing time, and region than the 14 carat alloy that it acquires one of
susceptibility to overageing and softening. Alloy addi- the characteristics of type III alloys, namely, it is very
tions of zinc also have an effect in changing properties susceptible to hardening on air cooling and must be
on converting between 14 and 10 carat because zinc effectively quenched on annealing if subsequent for-
tends to reduce the volume of the immiscibility field, ming operations are intended.
and the absolute zinc content increases with conver-
18 Carat Coloured Alloys
sions which maintain the same relative proportions of
the alloying elements (silver, copper, and zinc). On the 18 carat section in Figure 4 it will be noted
that the immiscibility field occupies a much smaller
At 10 carat, type III alloys are not in general use
area of the solid state field than at lower caratage.
because they are too hard and difficult to anneal for
Also, the AuCu ordered phase of the gold-copper
practical fabrication and their colour is not attractive.
binary system intrudes into the ternary field. The
The compositions (weight per cent) of three typical
concept of alloy types used above in discussing 10 and
commercial 10 carat jewellery gold alloys are listed
14 carat alloys is far less useful at 18 carat. For exam-
below:
ple, a copper-rich alloy in the Ag' range correspon-
Code Au Ag Cu Zn Ag'% Type ding to type I, which would be non age-hardenable
119 41.7 5.50 43.8 9.0 11 I and soft at 10 and 14 carat, is hardenable at 18 carat
226 41.7 11.70 40.8 5.8 22 II
due to the effect of the AuCu ordered phase. Alloys in
840 41.7 48.90 9.05 0.35 84 II
the Ag' range corresponding to type III, which are all
These alloys are based on the conversion of 14 carat hard at 10 and 14 carat, are only moderately hard and
alloys 116, 224, and 850 listed in Table I and have age-hardenable at 18 carat due to the restricted area of

72
the immiscibility field, and behave more like type II 18 carat fall within the Ag' range of type III alloys at
alloys do at 1.0 and 14 carat. Soft and non age- 10 and 14 carat, but behave like 14 carat type II alloys
hardenable alloys are found in the range of Ag' do as indicated above.
greater than about 75 per cent. Above 18 carat, the The compositions (weight per cent) of three typical
concept of type is not practically useful at all. In this 18 carat jewellery alloys are listed below:
range, the alloys both annealed and heat treated are
Colour Code Au Ag Cu Ag'%
progressively softer with increasing gold content and
Red 200 75 5 20 20
approach the properties of 24 carat or pure gold. Yellow 600 75 15 10 60
If one refers to the colour diagram in Figure 5, and Green 900 75 23 2 90
imagines lines drawn from the gold corner through
the intersection of the colour boundaries with the 18 The red alloy 200 responds to hardening on heat
carat line and then continued to the Ag' values on the treating (75 HR45T after solution annealing at
silver-copper axis it can be seen that at 18 carat, red 595°C followed by hardening at 260°C for 2 hours),
gold alloys occur in the Ag' range 0 to about 40 per although its position at 20 per cent Ag' in the 18 carat
cent, yellow alloys in the Ag' range 40 to 80 per cent, section of Figure 4 suggests that it might fall outside
and green alloys in the Ag' range from about 80 to the influence of both the ordered field and the im-
100 per cent. If one now observes where these ranges miscibility gap. The yellow alloy 600 can be treated
fall on the 18 carat quasi-binary section in Figure 4, to 66 HR45T by solution annealing at 650°C follow-
the following generalisations can be made: ed by precipitation hardening at 260°C for 2 hours.
All 18 carat green alloys behave like type I soft and The green alloy 900 is not precipitation hardenable.
non-precipitation hardenable alloys because their References
compositions fall well outside the immiscibility field. 1 `Metals Handbook', 8th edition, vol. 8, American Society for
There are no type I red alloys at 18 carat because at Metals, Metals Park, Ohio, 1973
2 J. Leuser, Metall, 1949, 3, 105-110, 128
low values of Ag' the ordering of the AuCu phase is 3 C. McCaul, R. Krahn and C. d'Antonio, Trans. Anz. Inst. Min.
available as a hardening mechanism. Yellow alloys at Metall. Eng., 1969, 245, 432-434
The second part of this article will be published in the October 1978 issue of Gold Bulletin.

The Thermal Conductivity of Gold

In low temperature equipment, thermal contact bet- scattering processes which generally show up between
ween solid state devices, thermometers etc. and the 0 (the Debye temperature, which for gold is about
surroundings may be limited by the conductance of 190 K) and O D/30. In impure metals, deviation arises
thin gold wires between them. Prediction of the thermal from the presence of minute amounts (— 10 ppm) of
conductivity of such wires at low temperatures is there- magnetic impurties (iron, chromium, manganese).
fore of importance. As a result of measurements reported Since at very low temperatures the electrical con-
by V. Novotny from the Department of Physics at the ductivity of pure metals is constant ('residual resistivity'),
University of Toronto(1), such prediction is now possible. the thermal conductivity should be proportional to tem-
The conduction of heat in gold is due almost ex- perature. This is actually observed, with ) = aT where
clusively to electrons, since phonons are effectively a = a TL,,. Where deviations due to the failure of the
scattered. This means that the two conduction processes — WF law occur, this relationship does not hold, and the
electrical and thermal, are very similar. In fact there thermal conductivity at low temperature can be written
exists a very simple relationship between the two, the as
Wiedemann-Franz (WF) law, established over a hundred 7=aT+ ßT' + YT' +
years ago. This is where ß and Y are small.
2/6T = L a Commercial gold wires are normally made from high
where A is the thermal conductivity purity gold, and Novotny found for the sample (diameter
or is the electrical conductivity 51 ± 1 µm; 99.7 per cent gold) studied by him that
T is the absolute temperature in degrees K the thermal conductivity was given by
and L o is the Lorenz number, which is a constant of
value 2.45 x 10 a WO/K`- Since the electrical 2=0.117T+7 x 10'T' (WK-'cm')
conductivity is much easier to measure, one may derive between 0.8 and 10 K.
the thermal conductivity of a metal from the above The data agree within 20 per cent with those calculated
equation, provided that no deviations from the WF law from the measured residual electrical resistivity using
occur. the WF law. This implies that predictions of the thermal
The WF law has been established, however, on the conductivity of other gold wires at low temperatures can
basis of elastic scattering. Although this is a good be made to within engineering accuracy over a wide
approximation for gold at temperatures below 10 K and range of residual resistance ratios.
above 300 K, between these temperatures the ratio I.K.
A/aT decreases, depending on sample purity. In pure Reference
metals, deviation arises from non- elastic electron-phonon 1 V. Novotny, Cryogenics, 1977, 17, 451-452

73