2.

15 Cryogenic Treatment of Engineering Materials

T Slatter, The University of Sheffield, Sheffield, UK
R Thornton, University of Leicester, Leicester, UK
r 2017 Elsevier Inc. All rights reserved.

2.15.1 Introduction 422

2.15.1.1 Links with Traditional Heat Treatment 422
2.15.1.2 A Brief History of Cryogenic Treatments 422
2.15.1.3 Industrial Context 423
2.15.1.3.1 The cryogenic processing industry 423
2.15.1.3.2 Current uses of CT processes 424
2.15.1.3.3 The future of CT and its applications 424
2.15.1.4 Cryogenic Treatment Processes 424
2.15.1.4.1 CT technology 425
2.15.1.4.2 CT processes 425
2.15.1.4.2.1 Case Study: Optimizing a CT process 426
2.15.2 Cryogenic Processing of Ferrous Alloys 426
2.15.2.1 State of the Art 427
2.15.2.1.1 Mechanical properties 427
2.15.2.1.2 Tribological performance 427
2.15.2.1.3 Mechanisms of microstructural change 429
2.15.2.2 Tool Steels 430
2.15.2.3 Plain Carbon Steels 434
2.15.2.4 Stainless Steels 435
2.15.2.5 Cast Irons and Pearlitic Steels 436
2.15.2.6 Case Studies 437
2.15.2.6.1 Impact wear resistance of low carbon steel and lamellar graphite cast iron 437
2.15.2.6.1.1 Introduction 437
2.15.2.6.1.2 Impact wear 437
2.15.2.6.1.3 Experimental details 437
2.15.2.6.1.4 Results 437
2.15.2.6.1.4.1 Specimen overview and wear scar morphology 437
2.15.2.6.1.4.1.1 Untreated specimens 437
2.15.2.6.1.4.1.2 Cryogenically processed specimens 438
2.15.2.6.1.4.1.3 Wear scar measurement 439
2.15.2.6.1.4.1.4 Estimation of wear scar volume 440
2.15.2.6.1.4.1.5 Comparison with a ‘traditional’ heat treatment process 441
2.15.2.6.1.5 Summary 442
2.15.2.6.2 Sliding wear resistance of pearlitic brake disk materials 442
2.15.2.6.2.1 Introduction 442
2.15.2.6.2.2 Requirements of brake rotor materials 442
2.15.2.6.2.3 Experimental details 442
2.15.2.6.2.4 Results 443
2.15.2.6.2.4.1 Hardness 443
2.15.2.6.2.4.2 Wear testing 443
2.15.2.6.2.4.3 Microstructural observations 443
2.15.2.6.2.5 Summary 444
2.15.3 Cryogenic Processing of Nonferrous Alloys 445
2.15.3.1 State of the Art 445
2.15.3.2 Aluminum Alloys 447
2.15.3.3 Magnesium Alloys 448
2.15.3.4 Titanium Alloys 448
2.15.3.5 Cobalt-Bonded Tungsten Carbides 449
Acknowledgments 451
References 451
Relevant Websites 453

Comprehensive Materials Finishing, Volume 2 doi:10.1016/B978-0-12-803581-8.09165-7 421

422 Cryogenic Treatment of Engineering Materials
2.15.1 Introduction
The term ‘cryogenic’ pertains to something at or causing the
creation of very low temperatures (typically o193 K/
80 1C)
and has a wide variety of uses in medical devices, electrical
components, and superconductors used in fields such as
quantum physics. While low temperatures are indeed involved
in both instances, the term ‘cryogenic’ should not be used
when referring to the field of ‘cryonics,’ which is of course to
do with the preservation of living creatures beyond the help of
contemporary medicine.
In the context of this chapter, cryogenic processing is taken
to refer to a range of subzero heat treatments (cryogenic
treatments or cryotreatments (CTs)) that are applied to
materials with the aim of causing permanent microstructural
changes and corresponding changes in mechanical properties
and behaviors.
Closely related fields of interest, but distinct disciplines in
their own right, are those that include activities use cryogenic
fluids in conjunction with engineering materials and pro-
cesses. These can be classified into two broad categories:
1. The field of investigating the ‘performance of engineering
materials at cryogenic temperatures’ (e.g., space, electronics,
physics research, and indeed the cryogenic processing
equipment industry itself when designing the equipment to
perform cryogenic processing).
2. The ‘use of cryogenic fluids in manufacturing’ (e.g., cryo-
genic machining, cryo-rolling, cryogenic burnishing, and
cooling of operating industrial machines).
Both of these areas have crossover with cryogenic proces-
sing, for example:
• Studies that consider if materials retain their desired per-
formance at cryogenic temperatures may give insight into
what drives any changes observed even if those changes are
reversible (i.e., ‘disappear’) when the materials are returned
to ambient temperatures to be used.
• Studies that consider using cryogenic fluids as an alternative
to conventional coolant in machining processes may benefit
from an understanding of how much coolant could be used
for how long a process before the workpiece undergoes
unwanted changes.
It is this discipline of cryogenic processing that this chapter
considers but links to these complementary fields are noted
where necessary. The terms ‘cryogenic processing,’ ‘cryogenic
treatment’ and ‘cryotreatment’ are used interchangeably.
This chapter first presents an overview of the development
of cryogenic processing before reviewing the current state of
the art. Several case studies are presented to illustrate how one
might investigate the potential of cryogenic processing for a
particular application in more detail.
2.15.1.1 Links with Traditional Heat Treatment
Classical heat treatments, which include bulk heating and
cooling (quench hardening, tempering, and aging treatments)
as well as surface treatments (such as laser hardening and
induction hardening), are used widely throughout engineering
to modify the microstructure and the subsequent behavior of
metals. All of these methods involve subjecting a component
to a controlled cycle of heating and cooling and for classical
heat treatments the temperatures are always above 273 K. In
ferrous metals, heat treatments are often used to make the
materials harder in an attempt to improve their wear char-
acteristics without significantly modifying their bulk proper-
ties. There are many applications where this is required to
ensure a satisfactory lifetime of components and it is extremely
common to treat steel components such as camshafts, crank-
shafts, and gears.
Less widely used is the extension of ‘heat treatment’ to
cryogenic temperatures. Although routinely considered in the
design and manufacture of industrial equipment, especially
for use in medicine and the physical sciences, there is a smaller
volume of work where cryogenic temperatures are used
deliberately to positively modify the microstructure for
strength and wear resistance.
CT involves lowering the material to temperatures below
193 K and holding or ‘soaking’ for a defined period of time
before raising the material back to ambient temperature. The
objective of CT is therefore to cause permanent changes to the
microstructure of a material that enhances desired properties,
with minimal or insignificant adverse effects. The process
affects the entire cross-section of materials and components
and is often considered as a single additional stage to a con-
ventional heat treatment cycle (although, as discussed in
Section 2.15.1.3.2, for many tools and components CT is
already a part of the ‘conventional’ process).
By way of a simple example, in hardened steels, cryogenic
processing utilizes phase transformations that occur when the
material is ‘soaked’ by being cooled in a liquid nitrogen
(LN2) filled chamber for up to 72 h. It has been observed that
the combination of these phenomena give cryogenically pro-
cessed materials improved wear resistance, stress relief and
dimensional stability.1 The level of these improvements
depend on the exact cooling parameters of the processing. In
this context, CT can be considered as an extension of a classical
heat treatment cycle; extending the effects of quench hard-
ening and preparing steels for further carbide precipitation
during subsequent tempering.
Relatively little work has been conducted to investigate the
improvements that can, or cannot be made to the mechanical
properties of other engineering materials. Similarly there
is little information about the ability of materials subjected
to the process to resist different types of wear, with the
majority of studies to date focusing on the resistance of cryo-
treated materials to abrasive and adhesive wear, or in use as
cutting tools.
2.15.1.2 A Brief History of Cryogenic Treatments
The earliest examples of subzero temperature processing
comes from Swiss watchmakers. In the mid-nineteenth cen-
tury, they used to leave delicate gears and the materials for
watch parts buried in snow in mountain caves over the
winter, having noticed that this would make gears more
durable, and allow parts to be made with more precision as
the materials deformed less during machining. This enabled
 Cryogenic Treatment of Engineering Materials 423

them to produce more reliable and longer lasting time-
pieces.2 During the first half of the twentieth century tool and
die-makers began freezing their tooling as they realized they
could machine more parts per cutting edge than before. Some
aero-engine components and even cutlery started to be trea-
ted as well. Although much of the early work has been
overlooked in recent years, perhaps due to ‘political circum-
stances’ at the time, it is clear that cryogenic treatments were
widely used and studied in the USSR in the first half of the
twentieth century. In a translation of one of his works on the
subject, originally from 1946, Gulyaev3 clearly describes a
number of effects of cryogenic treatments on steels including
the martensite transformation, the effects of alloying, stabi-
lization of austenite, and the effects of cryogenic treatments
on high-speed steels and carburizing components. Many of
these are still the subject of debate amongst the scientific
community today.
During the Second World War, cryogenic processing was
widely utilized to enhance the wear resistance of mechanical
parts in machinery and vehicles, although notable research
into its effects were effectively suspended until the 1960s when
NASA engineers noticed that spacecraft parts exhibited differ-
ent properties after returning from space. Shortly afterwards,
in the 1970s and 1980s Dr. Randall Barron,4 along with
Charles Mulhern,5 conducted what are considered the first
contemporary research projects into the effects of deep cryo-
genic processing. In studies using lathe tools and abrasive wear
experiments on a range of ferrous alloys, Barron recorded
significant increases in wear resistance in some materials
(up to 718% in the case of AISI D2 steel) whereas in others
(AISI A2, A6, and T2 steels) cryogenic processing appeared to
have no effect.
2.15.1.3 Industrial Context
2.15.1.3.1 The cryogenic processing industry
While cryogenic processing has been used as an industrial
technique for over 80 years, arguably, a cryogenic processing
industry has only existed for around 40 years, as awareness
and understanding of cryogenic treatment has grown. While
the majority of established companies can be found in the
USA and the EU (primarily in the UK), interest in cryogenic
treatment is growing in rapidly developing, heavily industrial
economies such as India and China.
The oldest of these, 3001 Below Cryogenic Tempering
Services, Inc. was established in 1966 (as CryoTech), however,
the majority of cryogenic treatment companies have started up
in the past 30 years. The industry is therefore dominated by
small- and medium-sized enterprises (SMEs).
Cryogenic treatment companies offer a range of services,
including cryogenic nitrogen and helium treatments, thermal
cycling, as well as pre- and post-cryotreatment tempering of
finished parts and raw materials. A number of these companies
additionally supply cryogenic processing equipment, both to
industry and research institutions. Table 1 summarizes the
services offered by some of these companies, indicating typical
soaking temperatures (Ts), times (ts), treatment types, liquid
helium (LHe2) processing capabilities and an overview of the

Table 1 Examples of cryotreatment companies and their advertised service capabilities

Company (location) Soaking Time, ts (h) Treatment Liquid Equipment

temperature, types helium supplied
Ts,min (K) treatment

3001 Below Cryogenic 88 72 (total N2 atmosphere No Model 921 processor:

Tempering process) electrical and nitrogen
Services, Inc. (Illinois, cooling, 682 kg capacity,
USA) Est. 1966 2.5 kW
Controlled Thermal 88 n/a Air cooled by heat Yes Applied Cryogenics, Inc
Processing, exchange with processors: 0.2–1.2 m3
Inc. (Illinois, USA) (liquid tempera- capacity, post-cryo
Est. 1980 ture) LN2 tempering, 4.4–11 kW
CryoPlus, Inc. (Ohio, 88 10 Pre-cryo temper; No n/a
USA) LN2 spray
Est. 1994 (vaporizes)
Cryogenic Institute of 88 24 LN2 immersion Yes Batch and continuous
New England, cryogenic treatment
Inc. (Massachusetts, equipment: 88–878 K range
USA) Est. 2002
Cryogenic Treatment 78 24 N2 atmosphere; No n/a
Services Ltd. post-cryo temper
(Nottinghamshire,
UK) Est. 2004
Cryogenics Interna- 78 24–62 N2 atmosphere No Treatment systems up to
tional (Arizona, 0.8 m3 capacity
USA) Est. 1986
Frozen Solid 78 Material N2 atmosphere; Yes n/a
(Cambridgeshire, dependent post-cryo multi-
UK) Est. 1998 stage tempering
424 Cryogenic Treatment of Engineering Materials
equipment they offer. Given its scarce availability LHe2 is
offered on a limited basis for extremely low-temperature
(
269 1C) treatments.
It is interesting to note that the range of services offered by
these companies reflects the variety of results highlighted in
the published literature. In fact it is possible to relate most of
the differences between treatment parameters offered by these
companies with the microstructural changes of martensitic
steels by association with their temperature- or time-depen-
dence. These changes have been summarized in Table 2 for
reference.
Whereas the elimination of retained austenite is theoreti-
cally achieved once a material passes the martensite finish (Mf)
temperature, preparation of the material for the development
of smaller secondary carbides and nano-carbides is also time-
dependent, meaning both lower treatment temperatures and
longer soak times may have beneficial effects. In fact, as is
subsequently discussed, both these changes have not only
been shown to be time-dependent, but intrinsically linked.
The issue of pre- or post-cryotreatment tempering is material
dependent and related to the initial phase composition of any
treated material.
As a result of these factors no cryogenic treatment
company should offer a single, ‘one-size-fits-all’ CT service.
CT parameters should be varied to suit the material and
degree of microstructural change or performance required. For
large and repeated batches of materials or parts to be treated,
an optimized CT cycle may represent a significant saving
in terms of overheads and reduction in the quantity of cryo-
genic coolant required. Indeed, for the cryogenic processing
industry, it is in this optimization of processes where com-
mercial advantage and valuable intellectual property may lie.
However, the extensive materials characterization facilities
and high level of expertise required to determine the para-
meters of these optimal processes have so far prevented
acknowledged leaders in commercial cryogenic treatment
services from emerging.
Table 2 Summary of the dependence of microstructural changes
due to cryogenic treatment in ferrous alloys
Microstructural change Parameter dependence
Conversion of retained austenite Temperature only (theoretically)
to martensite
Precipitation of nano-carbides Time, temperature
Dispersion and refinement of Time, temperature
secondary carbides
Table 3 Summary of differences between research-led and commercial cryotreatment (CT) practices
Research
Varied CT parameters
Wide consensus around use of N2 atmospheric cooling for best
results
Recognition of need to understand CT holistically within heat
treatment cycles
Small batch sizes
2.15.1.3.2 Current uses of CT processes
Cryogenic treatment companies (such as those mentioned in
Section 2.15.1.3.1) are involved in a combination of com-
mercial processing and after-market treatments, with the for-
mer becoming increasingly more significant. Although initially
CT services were applied almost exclusively to products in their
finished forms, it has increasingly become part of larger
manufacturing chains; an example of this being the treatment
of cutting tool inserts prior to coatings being applied, as CT
has been shown to have adverse effects on coatings such as
TiN.6 However, products such as brake disks, sports equip-
ment, and audio cabling are often still treated in their finished
forms or after partial disassembly.
Research-led and commercial CT practices differ sig-
nificantly, as highlighted in Table 3. Likely due to the basis of
many CT operations on purely anecdotal evidence rather than
rigorous analysis, there are a number of examples of ‘bad
practice’ within the commercial cryogenic processing industry,
from the point of view of the research community. These
include the restriction of cryogenic treatment parameters, the
use of anything other than nitrogen atmosphere cooling, and
the almost exclusive use of cryogenic treatment as an ‘after-
market’ process.
2.15.1.3.3 The future of CT and its applications
Although ferrous-based alloys feature in the bulk of cryogenic
processing research and constitute a significant portion of
commercial CT service requirements, a number of other
materials have also been shown to benefit from cryogenic
treatment. Aerospace materials such as aluminum, titanium,
and magnesium alloys represent a developing area for the
cryogenic processing industry, while sintered cobalt-bonded
tungsten carbide tool materials have also been shown to
respond favorably. Perhaps most unexpectedly, cryogenic
processing has also been shown to have beneficial effects on
nonmetallic composite materials, such as the polytetra-
fluoroethylene (PTFE)/Kevlar hybrid fabric.7
2.15.1.4 Cryogenic Treatment Processes
While subzero treatments of materials have arguably been
possible for centuries through the exploitation of naturally
occurring environmental conditions, cryogenic treatments
have only been practically possible since the liquefaction of a
number of important gases (notably nitrogen and helium) was
achieved in the late nineteenth century. Following the indus-
trialization of these processes in the first half of the twentieth
century cryogenic treatment started to be used on a significant
scale in manufacturing. Since then advances in insulation,
Commercial
Restricted treatment parameters, often only one fixed cycle offered
Varied cooling practices ((liquid nitrogen) LN2 immersion, LN2 spray, N2
atmosphere, and LN2 heat exchange with air)
CT typically applied as an ‘after-market’ process
Large batch sizes

temperature sensors, and digital controllers have allowed the
development of the efficient cryogenic processors used
commercially today.
2.15.1.4.1 CT technology
CT commonly involves a supply of LN2 into a thermally
insulated tank containing the parts or materials to be treated,
although specialist treatments are also available using LHe2.
The cryogenic fluid can be used in one of three ways: for direct
immersion of parts to perform a ‘cryo-quench’; as a working
fluid to cool air within the tank; or as a gas that that is cir-
culated by fans, thereby creating a ‘dry’ atmosphere.
The most common practice is to carry out CT using gaseous
nitrogen (N2) as the cooling medium. Figure 1 shows a sche-
matic diagram for such a setup in which LN2 is held in an
external tank or reservoir, before being vaporized, pumped into
an insulated chamber, and blown around the parts to be treated
by fans. The flow of nitrogen is controlled by the temperature
inside the chamber which is measured by thermocouples.
Cooling and heating rates in the chamber typically fall within
the range of 0.1–2.0 K/min.
Cryo-quenching (CQ) risks causing thermal shock,8 where
damaging thermal stresses are established by large temperature
gradients between the surface and bulk of a material, while
cryogenic cooling of air can lead to the build-up of vapor-ice
on the surfaces of components, unless all moisture can be
removed beforehand. Using N2 or helium creates a largely
inert atmosphere within the tank and has neither of these
drawbacks,9 while allowing for the controlled cooling of parts
and materials. Cryogenic treatments using LN2 and LHe2 are
theoretically able to reach 77 K (
196 1C) and 5 K
(
268 1C) respectively; the temperatures at which they boil.
Due to its abundance (making up 78% of the earth’s
Gas inlet
Nitrogen
reservoir
Gas outlet
Insulated treatment
chamber containing fans
and thermocouples
Figure 1 Schematic of equipment for cryotreatment using gaseous nitrogen cooling.
Cryogenic Treatment of Engineering Materials 425
atmosphere) nitrogen is commonly used in CT, whereas
helium is reserved for extremely specialized use.
The on-going development of cooling agents has led to the
establishment of different classifications of subzero treat-
ments. By soaking temperature these are either cold treatments
which can be achieved with dry ice (CT: 273–193 K), shallow
cryogenic treatments, (SCT: 193–113 K) or deep cryogenic
treatments (DCT: 113–77 K) which both require LN2.10
2.15.1.4.2 CT processes
Figure 2 illustrates the difference between CT cycles involving
CQ by LN2 and cooling or CT by N2 following on from a
regular heat treatment cycle in a typical quench-hardened
carbon steel, and preceding a post-treatment tempering cycle.
As cryogenic treatments are typically offered as an after-market
service, parts and materials are subjected to an indefinite
‘transition’ period between regular heat treatment and CT. In
reality, tempering may have been performed prior to cryogenic
treatment, which at best represents wasted process time and in
the worst case inhibits the effective application of cryogenic
treatment; such as when tempering may cause the decom-
position of retained austenite into cementite and ferrite.
The parameters that are typically controlled and varied
during CT are: cooling rate, soaking temperature, soaking time,
heating rate, and the position of the CT within the overall
treatment cycle in cases where materials or components are to
be tempered.
Compared to work performed to assess the improvement
in performance of cryotreated engineering materials, relatively
little work has investigated the influence of varying the para-
meters of the CT process itself. What work has been performed
typically limits the scope of the experiments to a single
material, varies either the temperature or duration at which the
Solenoid
Controller for
valve
programming
treatment cycles
Thermocouple feedback
Photographs courtesy of Cryogenic
Treatment Services Ltd.
426 Cryogenic Treatment of Engineering Materials
CT is performed and then assesses the improvement, or
otherwise, of a mechanical performance parameter.
In their early study on AISI T8 and AISI 1045 steels, Barron
and Mulhern5 determined that the greatest increase in wear
resistance for these materials could be achieved by using a low
cooling rate (6 K/min), a long soaking time (24 h), and a low-
temperature (77 K) soak. More recently, Darwin et al.11 uti-
lized Taguchi design of experimental methods, to determine
the significance of parameters in maximizing the wear resis-
tance of a high-chromium martensitic steel through deep
cryogenic treatment. They determined that the significance of
parameters was as follows: (1) soaking temperature, 72%; (2)
soaking time, 24%; (3) rate of cooling, 10%; (4) tempering
temperature, 2%; and that the tempering period was statisti-
cally insignificant.
One of the key commercial factors supporting the adoption
of CT is its relatively low cost, both in terms of the equipment
required and running costs per treatment cycle. Although a
Figure 2 Cryotreatment (CT) cycles illustrating liquid nitrogen
quenching and gaseous nitrogen cooling. The ‘Transition’ line indicates
an indefinite period of time for transport and storage prior to CT.
Figure 3 Schematic of (a) full heat treatment cycle, including deep cryogenic treatment, for AISI D2 tool steel and (b) detail of deep cryogenic
processing.13
number of companies treat small batches of finished compo-
nents for the automotive, aerospace, and manufacturing
industries, as well as treating more novel items such as sports
equipment. CT is not yet a widely used industrial process
despite reported evidence indicating substantial improvements
in wear resistance, hardness, and fatigue scatter reduction. The
reasons for this lie in the lack of any cohesive understanding of
the physical effects of CT on the microstructure and compo-
sition of treated materials, although a number of substantial
studies have been carried out.12
2.15.1.4.2.1 Case Study: Optimizing a CT process
In a recent example of this approach,13 simple rectangular
section specimens of a particular tool steel (D2) were treated
using a range of different soaking times at the cryogenic tem-
perature. The durations ranged from 0–84 h and all other
aspects of the treatment cycle remained uniform across the
specimens. These treatment cycles are illustrated in Figure 3.
The treated specimens were then subjected to a range of
microstructural analyses (e.g., SEM and XRD) and mechanical
tests (e.g., hardness, sliding wear) to assess the performance
variation as a result of the different process holding durations.
In this particular case it was found there was an observable
effect of soaking time on the precipitation of secondary car-
bides during subsequent tempering that lead to an improve-
ment in the hardness and an increase in wear resistance. In all
cases it was found that there is an optimum value for the
duration at which the specimens were held at the cryogenic
temperature.
2.15.2 Cryogenic Processing of Ferrous Alloys
Ever since its inception as a processing technique, ferrous
alloys (and in particular, tool steels) have dominated both
research and commercial uses of cryogenic treatments. This is
due to the responsiveness of hardened steels to cryogenic

treatments that are often able to transform the majority of any
retained austenite to martensite. In contrast to the reduction of
retained austenite that can be achieved through tempering
processes, by forming martensite at cryogenic temperatures
better dimensional stability can be achieved.14 Following
hardening and cryogenic treatments it is usually preferable to
temper the material to soften the virgin martensite and
improve toughness, in line with conventional practice.
Cryogenic treatments have also been shown to cause addi-
tional effects in carbon steels. Of greatest focus within the
research community has been the influence of cryogenic treat-
ments on the formation of nano-carbide precipitates during
tempering that further increase the wear resistance of tool steels.
However, further effects have been seen in non-hardened pear-
litic steels, cast irons, and stainless steels as well. A chronological
summary of the relative changes in the properties and behavior
of ferrous alloys due to cryogenic treatments is presented in
Table 4. Immediately apparent is the vast range of effects reported
in the scientific literature, that in turn, explains the range of
different treatment processes on offer by commercial businesses.
This section identifies the state of the art and trends in
performance modification that can typically be achieved by
subjecting ferrous metals to cryogenic processing. Following
this review, a selection of case studies are presented giving
specific examples as to the effects cryogenic treatments have on
the main ferrous alloy groups.
2.15.2.1 State of the Art
2.15.2.1.1 Mechanical properties
Although, from an engineering design perspective, the rigorous
characterization of the influence of cryogenic treatments on
the mechanical properties of materials may be desirable, stu-
dies that focus on strength, fatigue life, and toughness are few
and far between. Hardness is the exception to this rule, with
studies reporting changes due to CTs of up to 159%.38 As
hardness is commonly used as a proxy for yield strength, it
might be reasonably expected that reported changes in the
strength of cryotreated materials may change by similar values.
However, this is not the case, with most investigators reporting
no change in strength (yield or tensile) against one isolated
case where a 16% increase was observed,38 although it should
be noted that very few of the studies surveyed considered
strength as a separate parameter.
When it comes to reported values of impact energy (or
notch-toughness) and fracture toughness, the results are per-
haps surprising. While most investigators report significant
decreases in the ability of hardened ferrous alloys to absorb
energy following cryogenic treatments, studies involving AISI
H13 hot work tool steel goes against this trend, with notice-
able increases in fracture toughness reported.18,43 The rea-
soning given for this increase is contradictory with previous
work demonstrating greater brittle behavior in cryogenically
treated AISI D2 tool steel, with both sets of investigators
claiming that the fine carbide dispersion that results from
cryogenic treatment and tempering is responsible. In their
work on AISI D2 tool steel, Das et al.30c point to evidence of
microvoids formed by the decohesion of secondary carbides
on fracture surfaces (Figure 4).
Cryogenic Treatment of Engineering Materials 427
2.15.2.1.2 Tribological performance
The majority of research into the effects of CT on the tribo-
logical performance of ferrous alloys focuses on their abrasive
wear resistance in dry sliding conditions due to its wide rele-
vance to industrial cutting processes and mechanical contacts
founding in automotive and manufacturing fields. Beginning
this vein of research is arguably the wide-ranging study by
Barron, whose abrasive wear tests on 12 tool steels, three
stainless steels and four others having been subjected to both
shallow cryogenic treatment (SCT: 189 K) and deep cryogenic
treatment (DCT: 77 K), illustrated the huge potential, as well
as the significant variation, of this technique. Reporting an
improvement in sliding wear resistance of 718% (in the case of
AISI D2 tool steel after DCT) to the lack of any change in
several others (AISI A2, A6, and T2 tool steels), this study by
Barron lead to numerous others in which investigators con-
sistently reported extreme performance improvements in some
cases and no effect in others, leading Gill et al.12 to comment
that ‘the reported magnitudes of the enhancement in wear
resistance and the proposed governing mechanisms for such
enhancement do not provide any unified picture.’
However, since then understanding has developed and it is
clear now that the range of reported changes in the tribological
performance of cryogenically treated ferrous alloys arises from
the different microstructural changes that occur depending on
the chemical composition and heat treatment history of the
material. The most widely reported of these is the reduction or
elimination of retained austenite from hardened steels44 and
its transformation to martensite. Without subsequent tem-
pering this alone may lead to an increase in measured hard-
ness, but a significant decrease in toughness. This effect should
be seen in any hardenable steel (40.3 wt%C) where the
hardening process does not result in the complete transfor-
mation of austenite to martensite.
Also commonly reported is the appearance of numerous
small carbides following cryogenic treatment and tempering.45
These act to prevent dislocation movement and therefore inhibit
local plastic deformation (increasing matrix hardness) while
providing greater abrasive wear resistance. The prevalence of
these carbides is linked to excess carbon that exists in the matrix
following cryogenic treatment and the availability of carbide
formers, and hence is seen most clearly in steels that contain
significant quantities of alloying elements such as chromium,
tungsten, and molybdenum, which are used heavily in cold
work (AISI D-type) and high-speed (AISI M-type) steels.
Finally, and least frequently reported, is the effect that cryo-
genic temperatures have on dislocation density and movement
during the thermal deformation that occurs (for a detailed dis-
cussion see Gavriljuk et al.46 and Tyshchenko et al.47). Although
not reported on as yet, it could reasonably be theorized that this
effect may occur in other multiphase (e.g., ferritic–pearlitic)
steels where each phase possesses different thermal expansion
coefficients, resulting in additional stresses between them. This is
known to be the case in the hardened steels, where the mar-
tensite formed during cryogenic treatment has different lattice
parameters than that formed during the quenching process.48
Ultimately, these changes manifest as a change in hardness18,30a
that increases resistance to abrasion.
The combination of these effects is therefore what causes
the wide range of variation reported in the tribological
428 Cryogenic Treatment of Engineering Materials

Table 4 Chronological overview of changes in material properties due to cryogenic treatments (1973–2015). (Need interpretation of data in the
fourth column, especially when it is
38%/
38%)

Investigators Material Property ‘Best’ change

Barron4a 1) REX-AAA high-speed steel/ Impact energy 1)
38%/

2) REX-95 high-speed steel 2)
38%
Barron, Mulhern5 1) AISI T8 tool steel/ Wear resistance 1) þ 140%/
2) AISI 1045 carbon steel 2) þ 40%
Barron4b AISI D2 tool steel Wear resistance þ 718%
AISI S7 tool steel þ 403%
AISI O1 tool steel þ 172%
AISI A10 tool steel þ 165%
AISI M1 high-speed steel þ 125%
AISI H13 tool steel þ 109%
AISI T1 tool steel þ 76%
AISI 440 martensitic stainless steel þ 21%
AISI M2 high-speed steel þ 20%
AISI 430 ferritic stainless steel þ 20%
AISI 8620 NiCrMo alloy steel þ 12%
AISI 303 austenitic stainless steel þ 11%
AISI CPM10V tool steel þ 31%
AISI A2 tool steel þ 12%
AISI P20 tool steel –3%
AISI 1020 carbon steel
3%
AQS Meehanite graphitic cast iron
4%
Collins and Dormer 15
AISI D2 tool steel Hardness þ 6%
Wear resistance þ 6%
Impact energy
24%
Yun et al.16 AISI M2 high-speed steel Hardness þ 3%
Wear resistance þ 20%
Mohan Lal et al.17 1) AISI D3 tool steel/ Wear resistance 1) þ 175%
2) AISI M2 high-speed steel 2) þ 135%
Molinari et al.18 AISI M2 high-speed steel Hardness þ 8%
Wear resistance þ 51%
Molinari et al.18 AISI H13 tool steel Hardness þ 7%
Fracture toughness þ 15%
Bensely et al.19 En 353 (case carburized) steel Hardness þ 3%
Wear resistance þ 372%
Bensely et al.20 En 353 Hardness þ 3%
Wear resistance þ 867%
Liu et al.21 High-chromium cast irons Hardness þ 57%
Wear resistance þ 15%
Preciado et al.8 1) 0.18%C case carburized gear steel/ Hardness 1) þ 17% /
2) þ 6%
2) 0.14%C case carburized gear steel Wear resistance 1) þ 25% /
2) þ 19%
Yang et al.22 13Cr2Mn2V white cast iron Hardness þ 9%
Wear resistance þ 9%
Bensely et al.23 815M17 case carburized steel Strength
2%
Firouzdor et al. 24 AISI M2 high-speed steel drills Tool-life þ 126%
Vimal et al.25 En 31 steel Hardness þ 25%
Wear resistance þ 102%
Dhokey et al.26 AISI D3 tool steel Hardness 0%
Wear resistance þ 1257%
Akhbarizadeh et al. 27
AISI D6 tool steel Hardness þ 5%
Wear resistance þ 68%
Wang et al.28 High-chromium cast iron Hardness þ 15%
Wear resistance þ 19%
Baldissera et al.29 AISI 302 stainless steel (solubilized and Hardness 0%
hardened)
Strength 0%
Fatigue life þ 7%
Corrosion resistance 0%
(Continued )
 Cryogenic Treatment of Engineering Materials 429

Table 4 Continued

Investigators Material Property ‘Best’ change

Das et al.30 AISI D2 tool steel Hardness þ 8%

Wear resistance þ 257%
Fracture toughness
7%
Li et al.31 1) Cr8Mo2SiV die steel/ Hardness 1) þ 5% /
2) þ 6%
2) Cr12MoV Impact energy 1)
42% /
2)
38%
Jaswin et al.32 1) En52/ Hardness 1) þ 86% /
2) þ 12%
2) 21–4N valve steels Wear resistance 1) þ 42% /
2) þ 24%
Koneshlou et al.33 AISI H13 tool steel Hardness þ 20%
Wear resistance þ 67%
Slatter et al.34 1) EN-GJL-250 gray cast iron/ Wear resistance (impact) 1) þ 200%/
2) EN 1A mild steel 1) þ 400%
Thornton et al.35 SAE J431 G10 gray cast iron Hardness þ 2%
Wear resistance þ 81%
Amini et al.36 80CrMo12 5 tool steel Hardness þ 16%
Wear resistance þ 65%
Impact energy 0%
Gill et al.37 AISI M2 high-speed steel Hardness þ 8%
Wear resistance þ 58%
Kang et al.38 Fe75Ni25 alloy Hardness þ 159%
Strength þ 16%
Wear resistance þ 56%
Sri Siva et al.39 100Cr6 bearing steel Hardness þ 18%
Wear resistance þ 37%
Thornton et al.40 1) EN10083 C50R pearlitic steel/ Hardness 1) þ 28% /
2) 0% /
3) þ 4% /
4) þ 2%
2) AISI A2 tool steel (annealed)/
3) AISI D6 tool steel (annealed)/ Wear resistance 1) þ 23% /
2) þ 26% /
3) þ 30% /
4) þ 31%
4) AISI M2 tool steel (annealed)
Yan et al.41 W9Mo3Cr4V high-speed steel Hardness þ 2%
Wear resistance þ 240%
Sri Siva et al.42 100Cr6 bearing steel Wear resistance þ 52%
Perez et al.43 AISI H13 tool steel Hardness 0%
Strength 0%
Fracture toughness þ 24%

behavior of ferrous alloys following cryogenic treatments. A
significant body of work, which is therefore yet to be con-
ducted, is the correlation of chemical and phase composition
with pre- and post-cryotreatment heat treatment history with
the resulting changes in tribological performance that would
enable optimized cryogenic treatment cycles to be developed
‘depending on the needs of the application’ of the material.
This is not a trivial endeavor and will require a concerted
and coordinated effort between academic investigators and
industrialists.
2.15.2.1.3 Mechanisms of microstructural change
As previously discussed, in ferrous alloys the changes in
material properties and behaviors due to cryogenic treatments
are thought to result from:
• The transformation of retained austenite to martensite in
hardenable steels.44
• The precipitation and dispersion of fine carbides in steels
with greater excess carbon and strong carbide forming
alloying elements.45
• The movement and distribution of dislocations during
thermal deformation.46–47
Higher carbon and higher alloy content steels have lower
martensite start and finish temperatures (as illustrated
in Figure 5), meaning that quenching processes alone cannot
convert all of the austenite to martensite. Following quench-
ing, the retained austenite is unstable and can decompose into
martensite as a result of the thermal stresses resulting from
cryogenic treatments, or the diffusion of excess carbon occur-
ring during tempering.
430 Cryogenic Treatment of Engineering Materials

1. Cleavage facets in primary carbides.

2. Cracking of primary carbides
3. Cracking at the interface between primary carbides
and matrix.

White arrows indicate microvoids formed by decohesion

of secondary carbides.

Figure 4 SEM micrographs of fracture surfaces of AISI D2 steel as observed by Das et al.30c

marked rise in the proportion of fine carbides following

Figure 5 Effect of carbon content in steels on martensite start and
finish temperatures.3
cryogenic treatment and tempering (Figures 6 and 7) that is
dependent on the cryogenic treatment temperature. This is
thought to result from the distortion of the lattice structure,
during cryogenic treatment, which leads to dislocation con-
centrations that carbon atoms may diffuse to during sub-
sequent tempering.50 The small size of these precipitates is
explained by the comparatively low temperatures of temper-
ing, the short time available for diffusion and the local avail-
ability of carbide forming elements.
The recent work of Tyshchenko et al.47 and Gavriljuk et al.46
explains the proposed process in more detail. Tyshchenko
highlights that carbon atoms at cryogenic temperatures will be
effectively immobile and hence unable to form the con-
centrations necessary for the formation of new precipitates
while Gavriljuk suggests that the necessary carbon concentra-
tions are formed by the plastic deformation of martensite at
cryogenic temperatures. The transport of carbon atoms is
facilitated by the movement of dislocations that underlies this
deformation. It is therefore the time-dependent movement of
dislocations that causes the relationship between the duration
of the cryogenic treatment and the number of fine carbides
subsequently precipitated during tempering (and therefore,
the extent of change in performance seen in steels with strong
carbide forming characteristics).

2.15.2.2 Tool Steels

In their studies, Das et al.30a,45,49 have thoroughly char-
acterized the effects of cryogenic treatment on the micro- By a significant margin, the majority of studies involving
structure and properties of AISI D2 tool steel, illustrating a cryogenic treatments have concerned its application to tool

steels. In this section its effects on these widely used materials
are briefly reviewed. Cutting tools are required to machine a
wide range of materials including woods, polymers, light
alloys, cast irons and steels, hardmetals, and superalloys. The
properties of the material to be machined, the desired finish
Figure 6 Micrographs showing effects of (a) conventional, (b) 'cold,'
(c) shallow cryogenic, and (d) deep cryogenic treatments in AISI D2
tool steel.30a
Figure 7 Volume fractions of microstructural constituents following
conventional (CHT), 'cold' (CT), shallow cryogenic (SCT), and deep
cryogenic treatments (DCT) in AISI D2 tool steel.30a
Figure 8 Standard orthogonal cutting model.51
Cryogenic Treatment of Engineering Materials 431
and production rates all impact on the specific properties
required of cutting tool materials. As a result the range of
materials used to make cutting tools is extensive; however their
required properties fall into a manageable number of common
categories: strength, hardness, wear resistance, and thermal
stability.
Put simply, tool materials must be stronger and harder
than the materials they are intended to cut, while their prop-
erties must be sustained at the high temperatures they
experience during use. For this reason, changes in tool mate-
rials due to heat treatments should result in either thermo-
dynamically stable structures or structures that develop
beneficially upon heating (e.g., the ability of high-speed steels
to ‘run the temper’).
In the case of a typical orthogonal cutting process
(Figure 8), for example, the tool may wear by abrasion (flank
face), diffusion (rake face), or by fatigue cracking and impact
(which results in notching or chipping of cutting edges).
Because of this combination of damage processes, a range of
strategies are needed to effectively prevent rapid tool wear. It
should therefore be noted that cryogenic treatments, however
effective for a particular material, are unlikely to present a
solution to all manner of cutting problems in isolation.
Therefore exploring coatings and cutting process optimizations
are also recommended.
It is often cited that the wear resistance of these classes of
materials needs to be improved as cutting and metal forming
tools are typically exposed to impact and sliding conditions.
Therefore much research effort has been expended in con-
ducting basic dry sliding wear tests in laboratory environ-
ments, for which it is easy to obtain specimens, conduct
experiments, and provide comparative data with that obtained
from industry. However, this also means that there is great
variation in the work presented in the literature and released
by industry as illustrated by the range of testing conditions
highlighted in Table 5. The significance of the tribological
conditions (load, sliding speed, and material pairing) applied
is typically not considered, even though this may have a sig-
nificant influence on the results.
Even today, tool steels likely account for the greatest
number of cutting tools produced globally. Using the primary
strengthening mechanisms of alloying (including chromium,
molybdenum, vanadium, and tungsten), control of grain size
432 Cryogenic Treatment of Engineering Materials

(through heat treatment), and due to carbide precipitations
these materials can be produced with a hardness up to 8 GPa
(815 HV) and thermal stability to 1000 1C.54
A typical heat treatment process for a tool steel will involve
austenitizing, quenching (rapid cooling by water, oil or gas),
and tempering. The quenching process is designed to cause as
complete a transformation of austenite to martensite as pos-
sible although, as previously highlighted (Figure 5), the high
alloy content of tool steels can lower the martensite finish
temperature to below ambient temperatures. Following
quench hardening, tempering serves two purposes. Firstly, to
cause the decomposition of retained austenite to martensite by
allowing the diffusion of excess carbon and secondly, to allow
for the nucleation and growth of carbide precipitates.
Even in the early works of Gulyaev,3 it had been established
that the sooner after quench hardening cryogenic treatment
could be applied, the greater the proportion of retained auste-
nite that could be converted to martensite. Yet today, cryogenic
treatment is still commonly conducted as an ‘after-market’
treatment on finished or semifinished components that may
have been heat treated hours, days or even months previously,
thus limiting the effectiveness of CT in this respect. Further-
more, to avoid austenite stabilization, cooling from the critical
temperature to cryogenic temperatures should be continuous.55
This is not the complete picture, however, as more recently it
has been suggested that there does exist a lower temperature
limit below which further transformation will not take place
and that a time-dependent isothermal transformation of
retained austenite to martensite may continue at cryogenic
temperatures. Studying the behavior of X153CrMoV12 powder
metallurgy steel using Mössbauer spectroscopy, Gavriljuk et al.46
demonstrated that cooling the material to
196 1C and soak-
ing for 96 h had no effect on martensite content, whereas
soaking at
150 1C did cause the transformation of retained
austenite. Findings such as these hint at substantial benefits still
to be obtained by optimizing CT processes, both in terms of
maximizing beneficial properties and minimizing process costs.
By reviewing the three most commonly tested tool steels
from the scientific literature (AISI D2, H13 and M2) some
further trends can be identified. Their nominal compositions
are given in Table 6.
Two robust studies of note, concerning the application of
cryogenic treatments to AISI D2 tool steel, are those by Collins
and Dormer15 and Das et al.30a,30b The treatment parameters
adopted by these investigators are summarized in Table 7.
In their study, Collins and Dormer illustrated two effects
influencing wear resistance following cryogenic treatment.
Firstly, the complete transformation of retained austenite to
martensite and secondly, the precipitation of secondary car-
bides following CTs. They determined that although a higher
austenitizing temperature (and therefore greater retained
austenite) leads to a greater hardness attainable with cryo-
genic treatment, the maximum wear resistance was found
following a lower temperature austenitization due to the
greater precipitation of secondary carbides during tempering.
Lower cryogenic treatment temperatures and longer soaking

Table 5 Wear testing conditions reported in a selection of studies on cryogenic treatments

Investigator(s) Sample Counterbody Test parameters

Shape Material Shape Material Normal Sliding Sliding

load (N) velocity distance
(m s
1) (m)

Barron4b Pin M1, M2, T1, Wheel Course grit 430 0.48 2160
T2, H13, D2, alumina
A6, A10, O1, grinding wheel
P20, S7, etc.
Collins and Block D2 Wheel Hardened D2 steel 21 0.50–3.62 200–600
Dormer15
Meng et al.48 Pin D2 Disk WC-coated En 35 49–78 1.50 900
steel
Molinari et al.18 Disk M2, H13 Disk Hardened 100Cr6 150 0.80 5000
Das et al.52 Pin M2, D3 Disk Grinding wheel 20–50 0.18–0.6 324–1080
Rhyim et al.53 Pin M2 Disk Alumina abrasive 10 0.11 3.22
paper
Gill et al.37 Pin M2 Disk En 32 49–88 1.5 1800

Source: Adapted from Das, D.; Dutta, A. K.; Ray, K. K. On the Enhancement of Wear Resistance of Tool Steels by Cryogenic Treatment. Philos. Mag. Lett. 2008, 88 (11), 801–811.

Table 6 Compositions of commonly cryotreated AISI tool steels reported in the literature (P, S omitted; balance Fe)

wt.% C Si Mn Cr Mo V Other

AISI D2 1.40–1.60 0.60 0.60 11.00–13.00 0.70–1.20 1.10 1.00Co

0.25Cu
AISI H13 0.32–0.45 0.80–1.20 0.20–0.50 4.75–5.50 1.10–1.75 0.80–1.20 0.25Cu
AISI M2 0.86–0.94 0.45 maximum 0.40 maximum 3.80–4.50 4.70–5.20 1.70–2.10 5.90–6.70 W
 Cryogenic Treatment of Engineering Materials 433

Table 7 Heat treatment sequences applied to AISI D2 tool steel in Table 9 Heat treatment sequences applied to AISI H13 tool steel in
the studies of Collins and Das the study of Perez

Collins and Dormer15 Das et al.30 Perez et al.43

Hardening (Q) (1070, 1040, 1010, 1024 1C for 30 min Hardening (Q) 1020 1C – gas- 1020 1C – oil- 1020 1C – air-
970)1C – N2- – air-quenched quenched quenched quenched
quenched Tempering (T) 590 1C for 2 h
Tempering (T) 200 1C 210 1C for 2 h Cryotreatment (C)
196 1C for
Cryotreatment (C) (
196,
130,
80)1C (
196,
125, 12 h
for 30 min
75)1C for 36 h Treatment order QCTTT
Treatment order QCT QCT

influence the effectiveness of the cryogenic treatment the

Table 8 Heat treatment sequences applied to AISI H13 tool steel in
the studies of Molinari and Koneshlou
Molinari et al.18 Koneshlou et al.33
Hardening (Q) 1020 1C – vacuum- 1040 1C for 30 min
quenched – air-quenched
Tempering (T) 570 1C for 3 h 560 1C for 2 h
Cryotreatment (C)
196 1C for 35 h
196 1C for 8 h
Treatment order QTTC QTCT
durations were found to be beneficial both in terms of
maximizing wear resistance and minimizing loss of
toughness.
Subsequently Das et al. studied the wear behavior of AISI
D2 tool steel in more detail, having observed similar micro-
structural changes. Under pin-on-disk testing that resulted in
severe delamination of the material, they determined that the
increased wear resistance of the cryotreated samples was due to
their resistance to subsurface plastic deformation and therefore
resistance to white layer formation. While a more complete
transformation of retained austenite to martensite may result
in the highest bulk hardness, the fine carbide precipitates act to
limit dislocation movement further and therefore inhibit
plastic deformation.
The teams lead by Molinari18 and Koneshlou33 have stu-
died the mechanical properties of AISI H13 tool steel in some
detail, adopting very similar heat treatment parameters but
with different treatment cycle orders (Table 8). While Molinari
et al. applied cryogenic treatment as a final step, Koneshlou
et al. tempered the material both before and after CT. The
difference in material properties developed was significant,
with Molinari et al. reporting no change in hardness while
Koneshlou et al. observed a hardness change of 20% (49
HRC–5 HRC) following cryogenic treatment. It seems likely
that this marked difference resulted from the quantity and
stability of retained austenite remaining prior to cryogenic
treatment; in the case of Molinari et al. the double tempering
cycles will likely have resulted in the decomposition of the
austenite.
More recently Perez et al.43 have also studied how cryogenic
treatments affect the mechanical properties and fracture
behavior of AISI H13 tool steel. Of particular interest in their
study was the influence of the rate of the initial cooling, which
they varied through the use of different quenching media
(Table 9). Although the rate of initial cooling did not appear to
application of the subzero treatment had a pronounced effect
on fracture toughness, resulting in a greater than 20%
improvement. Fractography suggested that the presence of a
uniform distribution of fine carbides in the cryotreated sam-
ples had resulted in a more ‘ductile’ fracture behavior, based
on the growth and linking of microcavities, in comparison to
the brittle fractures that resulted from the stress concentrating
effect of more coarse carbides that are otherwise present in the
material. The corresponding reduction in carbon content of
the martensite, following cryogenic treatment, also contributes
to a tougher matrix.
Studies involving AISI M2 high-speed steels present some
mixed results. Even as early as the work of Gulyaev, variations
in improvements in high-speed steel tool lives following
cryogenic treatments had been reported between 40–400%.3
More recent investigators have reported modest increases in
hardness16,18,37 along with significant improvements in
toughness16,18 and wear resistance.18,37 In common with other
studies involving tool steels, the hardness changes are not
proportional to increases in abrasive wear resistance, indicat-
ing multiple contributing microstructural factors. However,
beyond the conversion of retained austenite to martensite the
other changes are less clear.
Treatment cycles adopted by recent investigators have var-
ied widely. Yun et al.16 explored the effects of varied duration
and cyclic cryogenic treatments (Table 10), as well as its
effectiveness after tempering had already been carried out.
They determined that cycling cryogenic treatment had a greater
effect than simply extending its duration, while CT following
tempering still resulted in modest changes in material prop-
erties. Hot hardness was found to improve markedly that was
argued to result from the formation of sub-nanometer (30-
–60 Å ) carbides on twinning surfaces and other crystal-
lographic defects during cryogenic treatment. Upon heating
these carbides were able to grow further and compensate for
the thermal effects on the matrix.
By contrast Molinari et al.,18 who also studied whether
cryogenic treatment was most effective before or after temper-
ing, and to what degree tempering should be done (Table 11),
came to different conclusions. While noticeable changes in
hardness, strength, toughness, and wear resistance were repor-
ted, they observed no change in carbide distributions and even
‘tempered martensite de-twinning’ following cryogenic treat-
ment. The most effective treatment was deemed to be applying
cryogenic treatment following double tempering – based on
other studies this would likely have resulted in a tougher
material with moderately increased hardness.
434 Cryogenic Treatment of Engineering Materials

Table 10 Heat treatment sequences applied to AISI M2 tool steel in the study of Yun

Yun et al.16

Hardening (Q) 1250 1C

Tempering (T) 560 1C
Cryotreatment (C)
196 1C for 24 h
196 1C for 48 h
196 1C totaling 48 h
196 1C for 48 h
Treatment order QCTTT QCTTT QCCCTTT QTTTC

Table 11 Heat treatment sequences applied to AISI M2 tool steel
in the study of Molinari
Molinari et al.18
Hardening (Q) 1220 1C – vacuum-quenched
Tempering (T) 550 1C for 2 h
Cryotreatment (C)
196 1C for 35 h
Treatment order QTTC QCT QCTT
Table 12 Heat treatment sequences applied to AISI M2 tool steel
in the study of Gill
Gill et al.37
Hardening (Q) Unspecified
Tempering (T) 150 1C
Cryotreatment (C)
110 1C for 18 h
196 1C for 38 h
Treatment order QCTT
More recently Gill et al.37 focused on the influence of
cryogenic treatment temperature, with only a low-temperature
temper applied subsequently (Table 12). They determined that
hardness was most significantly improved by shallow cryo-
genic treatment (
110 1C for 18 h) while wear resistance
benefitted substantially from deep cryogenic treatment for a
longer period (
196 1C for 38 h). It was proposed that
stresses from the austenite transformation, during cryogenic
treatment, result in greater twinning and dislocations; defects
to which alloying elements segregate during tempering. The
lack of diffusion at cryogenic temperatures results in greater
lattice distortion and decreased stability of the martensite, in
comparison to that formed through tempering alone. This
corresponds closely with the prevailing understanding Gulyaev
described at the time.3
What is clear from the plethora of studies concerning
cryogenic treatment of tool steels is that it can have very
substantial (and often substantially beneficial) effects on their
properties and in-service performance. However, care needs to
be taken to treat tool steels appropriately to maximize the
specific qualities required.
For instance, if maximum hardness is required a shallow
cryogenic treatment applied immediately following high-
temperature austenitization may provide best results. If great-
est toughness is needed then perhaps the steel should be first
tempered before deep cryogenic treatment to encourage a
ultrafine carbide precipitation. As tool-life requires resistance
to a combination of wear mechanisms, it may be preferable to
perform a medium temperature austenitization followed by
quench hardening, multiple deep cryogenic treatment, and
tempering cycles.
Defining and expressing the relationships that allow the
optimum cycle parameters to be applied, depending on
material and application conditions, seems to be the next big
challenge in this field.
2.15.2.3 Plain Carbon Steels
In contrast to the wealth of research involving high alloy
content tool steels, there is relatively little concerning the
effects of cryogenic treatment on ‘plain’ or low-alloy content
carbon steels. As such it is difficult to draw strong correlations
from the results and observations reported. Instead, more
general findings are highlighted with the compositions of
those steels reported in literature given in Table 13.
Gulyaev3 made specific reference to the likely effectiveness
of cryogenic treatments on plain carbon steels, suggesting that
they would be entirely ineffective on steels with o0.6%C
as their martensite finish temperature lies above 0 1C (see
Figure 5). However, Gulyaev also highlighted that even small
amounts of alloying additives can significantly reduce the
martensite finish temperature. At the time, cold treatment of
carburizing steels was more common than for high-speed
steel, as the carburized (higher carbon content) layer retains
more austenite during quenching.
In some of their early work, Barron and Mulhern5 applied
varied CTs to AISI 1045 carbon steel, finding that there was no
measurable change in hardness but that the retained austenite
was almost completely converted to martensite. Modest
increases (B10%) were reported in wear resistance but there
was no visible carbide formation using optical microscopy.
Assuming the wear findings to be accurate, finer precipitates
may have developed and been responsible for the change in
wear resistance.
The same observations were made by Bensely et al.19
when testing the effect of cryogenic treatments on carburized
En 353 low-alloy steel (with notable Cr and Ni, but lower C
content). Although the retained austenite was largely con-
verted to martensite through CTs and optical microscopy
revealed no change in carbide precipitation, increases in
wear resistance of up to 372% were reported. The authors
attributed this improvement to fine carbide precipitates that
they assumed were present. Although the carburized gear
steels used by Preciado et al.8 were very similar in compo-
sition, significant hardness increases (up to 17%) in the near
surface region were reported alongside much more modest
(up to 25%) increases in wear resistance. In this case only a
low-temperature (150 1C) temper was conducted. Although
the wear testing conditions of each study are difficult to
 Cryogenic Treatment of Engineering Materials 435

Table 13 Compositions of plain and low-alloy carbon steels reported in the literature (P, S omitted; balance Fe)

wt.% C Si Mn Cr Mo Ni Other
5
AISI 1045 0.45 0.20 0.70 0.05 0.01 0.02 0.01Cu
En 35319 0.17 0.19 0.92 1.09 0.11 1.05 –
0.18 C steel8 0.15–0.21 0.15–0.40 0.60–0.90 0.85–1.15 0.15–0.25 – –
0.14 C steel8 0.11–0.17 0.15–0.40 0.30–0.60 0.80–1.10 0.20–0.30 3.00–3.50 –
En 3125 0.96 0.21 0.57 1.09 – – –

Table 14 Compositions of stainless steels reported in the literature (P, S omitted; balance Fe)

wt.% C Si Mn Cr Mo Ni Other

AISI 3034b 0.08 1.00 2.00 18.00 – 8.00 –

AISI 4304b 0.12 1.00 1.00 16.00 – 0.50 –
AISI 4404b 0.70 1.00 1.00 17.00 0.75 0.50 –
AISI 304L56 0.022 0.35 1.79 18.32 – 8.23 0.40Cu
0.08Co
0.055N
AISI 308L56 0.014 0.86 1.73 19.68 0.05 10.15 0.05Cu
AISI 30229 0.05–0.15 o2.00 o2.00 16–19 o0.80 6.00–9.50 –

compare (10 N on 6 mm diameter ball in the former and
60–80 N on 10 mm diameter flat-headed pin in the latter), it
could be speculated that the higher tempering temperature
used by Bensely softened the martensite formed during
cryogenic treatment while promoting a more significant fine
carbide precipitation. In Preciado’s study, the lower tem-
perature tempering may have allowed the martensite to
retain its hardness but prevented substantial precipitation of
fine carbides.
Vimal et al.25 experimented with a much higher carbon
(B1%) low-alloy steel, En 31. Varying the heat treatment
process order, with CTs before and after tempering, they
obtained the maximum hardness and wear resistance by
applying cryogenic treatments immediately after quenching,
but before tempering. Observations made suggested the
transformation of retained austenite and formation of fine
carbides were responsible.
Similarly to studies conducted on tool steels, those (few)
conducted on plain carbon or low-alloy steels allow some
practical suggestions to be made. Cryogenic treatment can
clearly be effective on these materials. However, if a significant
increase in hardness is sought, then the composition of the
material must be such that the martensite finish temperature is
significantly below 0 1C – this may be true in high-carbon
steels or those with strong austenite stabilizers such as Cr and
Ni. If wear resistance is to be improved then the quenching
and CT processes must result in excess carbide formers being
present in the microstructure that can then form precipitates
during tempering. Therefore low-alloy steels that contain
noticeable amounts of Cr or Mo may be suitable for this
treatment approach.
2.15.2.4 Stainless Steels
Stainless steels present an interesting ‘challenge’ when it comes
to assessing the effectiveness of cryogenic treatments. While
austenitic stainless steels are most common, the fact that they
can be produced as ferritic or martensitic materials, with or
without significant carbide precipitations arguably means they
cannot be treated as a single family of materials. However, the
limited quantity of published research involving these mate-
rials necessitates a combined approach. Table 14 summarizes
the compositions of the stainless steels subsequently dis-
cussed. It should be noted that the AISI 3XX stainless steels are
austenitic while the AISI 430 stainless is ferritic and the AISI
440 stainless is martensitic.
The earliest application of cryogenic treatments to stainless
steels can be found in Barron’s wide-ranging wear resistance
study4b in which, along with a number of other carbon, alloy,
and tool steels, AISI 303 (austenitic), 430 (ferritic), and 440
(martensitic) stainless steels were subjected to abrasive wear
testing. Although this was an unusual test for materials that are
typically not considered for their wear resistance, Barron’s study
indicated cryogenic treatment could affect any of these materi-
als, with reported increases in wear resistance of 10–20%. In the
case of the martensitic stainless steel, transformation of any
retained austenite was likely an influencing factor, although
with the other two materials it clearly could not have been. This
therefore indicates that other microstructural alterations (fine
carbide precipitations and/or change in dislocation character-
istics) are significant factors.
Despite these seemingly significant findings, very few sub-
sequent studies have involved stainless steels. Singh et al.56
investigated the application of cryogenic treatment in
improving the fatigue life of welded joints (AISI 308L)
between stainless steel (AISI 304L) plates. Under high-cycle
fully-reversed loading conditions, they concluded that the
strain-induced martensitic transformation, which occurred
during the CT process, resulted in compressive stresses that
effectively raised the fatigue limit of the joints; more than
doubling their fatigue lives in some cases.
Although this was another seemingly significant finding,
the next major study (and by far the most robust to date) was
that of Baldissera et al.29 who conducted a full factorial
436 Cryogenic Treatment of Engineering Materials
design of experiments approach to investigate the effects of
cryogenic treatments on the hardness, strength, fatigue life
and corrosion resistance of AISI 302 stainless steel. Different
cryogenic soaking temperatures and times, as well as the
effect of solubilization treatments were considered. CTs were
found to have no significant effect on the static mechanical
properties of the material, or its corrosion resistance under
salt-spray. However, deep cryogenic treatment (88 K) was
found to significantly improve the fatigue life of the solubi-
lized (but not hardened) samples. Fractographic analyses
revealed a number of small secondary cracks in the cryo-
treated material that could have originated from fine pre-
cipitates and acted to absorb energy from the cyclic loading
process, increasing the nominal stress intensity required for
crack initiation and therefore increasing the toughness of the
material.
Studies on stainless steels are too few for strong conclu-
sions to be drawn as to the possible benefits of cryogenic
treatments. However, it does appear that subzero treatments
may be effective at increasing the fatigue life of stainless steels
‘after certain types of treatments.’ Aside from being able to
convert retained austenite to martensite, if that is what is
desired, the changes in mechanical behavior reported to date
appear to relate to changes in precipitation behavior, with the
possibility of more subtle microstructural changes playing a
role as well.
2.15.2.5 Cast Irons and Pearlitic Steels
Two other interesting, overlapping groups when it comes to
the application of cryogenic treatments are ferritic and pearlitic
cast irons and steels. Although not considered in much of the
early work, over the past 10 years investigators have begun to
study these alloys more closely. The studies subsequently
reviewed involve the alloys summarized in Table 15.
There are currently just two groups of work in this field at
present. The first, involving the team of Liu,21 Yang,22 and
Wang28 et al., have worked extensively to characterize the
factors influencing the effectiveness of cryogenic treatments on
high-chromium (and therefore austenite retaining and carbide
forming) cast irons. More recently the present authors have
focused on ‘plain’ graphitic cast irons34,35 and pearlitic
steels.40,57
In their studies, investigators Liu and Yang et al. observed
that cryogenic treatments following subcritical heat treatments
were more effective than air cooling in transforming retained
austenite to martensite and promoting the formation of fine
Table 15 Compositions of cast irons and pearlitic steels reported in the literature (P, S omitted; balance Fe)
wt% C Si
14Cr2Mn2V21a 2.76 0.90
13Cr3Mn1.5V21b 2.82 1.24
14Cr4Mn0.5B21c 2.92 0.82
13Cr2Mn2V22 2.76 0.90
16Cr1Mo1Cu28 2.77 0.70
EN-GJL-25034 3.25 2.50
SAE J431 G1035 3.35–3.60 1.90–2.30
EN10083 C50R40 0.47 0.18
secondary (Fe, Cr)23C6 carbides in high-chromium cast irons.
While the maximum hardness ( þ 57%) of these materials can
be achieved by subcritical heating to around 550 1C before
quenching directly in LN2, the maximum wear resistance
( þ 15%) was obtained by heating to around 600 1C before
cryogenic quenching. The reported observations suggested that
while the lower temperature treatment resulted in a more
complete austenite to martensite transformation, the higher
temperature allowed for a greater precipitation and growth of
fine secondary carbides, which enhanced the abrasive wear
resistance further.
Using a very similar alloy to their colleagues’ previous
studies, Wang et al. further explored the influence of high-
temperature treatments on these alloys, with destabilization
treatments conducted at 900–1150 1C before air cooling
or cryogenic quenching. It was reported that secondary car-
bides were more uniformly distributed following cryogenic
treatment, while the proportion of martensite also increases. In
this case both maximum hardness ( þ 15%) and wear resis-
tance ( þ 19%) were found following cryogenic quenching
after destabilization treatment at between 1000–1100 1C.
In their recent studies, the present authors have concentrated
on characterizing the wear performance of cryogenically treated
gray cast irons and pearlitic steels under different dominant
wear mechanisms and contact conditions. Investigating the
effectiveness of cryogenic treatment on EN-GJL-250 gray cast
iron and EN1, a mild steel, Slatter et al.34 recorded 200% and
400% increases, respectively, in their resistance to wear under
repetitive hammering impact. Phase transformations were not
possible as the low-alloy content and slower cooling (in the
case of gray cast iron) prevents austenite being retained; it
decomposing to ferrite and cementite instead. No change in
precipitation behavior was observed either.
Conducting sliding wear tests on SAE J431 G10 gray cast
iron and EN10083 C50R pearlitic steel break disk materials,
Thornton et al.35,40 recorded significant increases in the wear
resistance of each material. In the case of gray cast iron this was
up to þ 81% at high contact pressures and low sliding speeds,
with negligible changes observed at low contact pressures and
high sliding speeds. While the hardness of the gray cast iron
was not affected by the CT, the hardness of the pearlitic steel
was found to have increased by around 20%. This was coupled
with a more consistent improvement in wear resistance of
15–20% across all contact pressures tested and visible signs of
a shift to a more brittle dominant wear mechanism (with more
extensive cracking and pitting visible in cryotreated speci-
mens). As with the previous study by Slatter et al., there were
Mn Cr Mo V Other
1.98 13.72 – 1.6 –
2.80 13.34 0.70 1.5 –
3.66 13.86 – – 0.5B
1.98 12.62 – 1.6 –
1.90 16.38 1.08 – 0.9Cu
0.50 – – – –
0.60–0.90 – – – –
0.75 0.03 o0.01 – 0.03Ni

no obvious microstructural changes to explain these changes.
Further analysis of the pearlitic steel using X-ray diffraction,
electron-backscatter diffraction, and transmission electron
microscopy ruled out the possibility of the presence and
transformation of small quantities of retained austenite or fine
carbide precipitations resulting from cryogenic treatments.57
These findings lead to the conclusion that a more fun-
damental change in the materials was responsible. It is
theorized that a change in dislocation distribution or density
due to the cryogenic treatment process could result in a
change in the residual stress state and therefore wear beha-
vior of the materials tested. These studies are further elabo-
rated upon as case studies that may provide outline
methodologies for assessing the basic tribological perfor-
mance of cryogenically treated ferrous alloys.
2.15.2.6 Case Studies
2.15.2.6.1 Impact wear resistance of low carbon steel
and lamellar graphite cast iron
2.15.2.6.1.1 Introduction
This case study outlines investigations into the influence of
cryogenic treatment on the impact wear resistance of low car-
bon steel and lamellar graphite cast iron. This has been selected
because it provides more detailed insight into the types of
mechanical performance improvement that can be seen with
cryogenic treatment of carbon steels and cast irons, and also
because there is very little literature that discusses the impact
wear resistance of cryogenically treated engineering materials. It
also provides a basic methodology that could be used for
assessing the potential using CT in a particular application.
2.15.2.6.1.2 Impact wear
Percussive impact wear mechanisms arise from two or more
bodies impinging normally or otherwise to each other. These
mechanisms typically involve elements of elastic and plastic
deformation, when impact energy is high and depending on
the ductility of the materials, and/or fatigue accompanied by
wear debris as a result of crack propagation. This mechanism is
commonly found in a great many mechanical devices.
Impact wear resistance of materials can be investigated in
numerous ways – by firing multiple projectiles being propelled
into a stationary target/specimen by gravity, a fluid stream, or
magnetic fields and in the case of single impact events a pro-
jectile fired by gas propelled barrel. That said, the majority of
the previous experimental work conducted in this area has
used a reciprocating hammer-type test rig to generate the cyclic
percussive impact and it is this type that was used here to
subject both untreated and cryogenically treatment specimens
to impact. These types of tests rigs are simple to design and
construct.
2.15.2.6.1.3 Experimental details
For the purpose of comparing results, it is important to char-
acterize the contact that is produced by the test rig geometry. In
this case, the rig impinged a 15 mm chrome steel ball normally
to the specimen surface at 10 Hz (impacts per second). The
striker had a closing velocity of 0.45 m s
1 and an impact energy
of 0.22 kJ. Applying analyses demonstrated by Goldsmith58 and
Cryogenic Treatment of Engineering Materials 437
Hertz59 the contact stress was calculated to be 1.8 GPa. The
material specification equivalent to that of the ball is EN 31 or
AISI 52100. The hardness of the balls was in the range of
700–900 HV with a maximum surface roughness of 0.125 mm.
The cast iron material used was EN-GJL-250 lamellar gra-
phite cast iron (average hardness of 235 HV) and the low carbon
steel used was EN 1A (average hardness of 175 HV).The form of
the specimens was circular disks, 50 mm in diameter, cut from
an as-cast bar of each material. For simple tests such as these it is
useful to keep the geometry of the specimens as simple as
possible as this allows isolation of the fundamental material
performance, aids comparison at a later date and makes creating
a robust dataset easier. Each specimen was cut and ground to be
10 mm thick with a uniform surface finish (0.5 mm).
Two sets of specimens were prepared for each material, one
set was cryogenically processed and the other set was left
untreated. To the naked eye, the specimens that were cryo-
genically processed were indistinguishable from those that
were left untreated and had similar macro-hardness. When
compared to the calculated contact stress of 1.8 GPa the
measured hardness values, and therefore the yield strength of
the materials tested, indicates that deformation of the material
in the contact zone is likely.
Both material types were subjected to identical cryogenic
processing using a cryogenic chamber similar to that described
in Section 2.15.1.4. All of the specimens were placed in the
chamber at room temperature and were then gradually cooled
down to
180 1C over a period of 4 h. The chamber was then
held at this temperature for 16 h to ensure uniform transfor-
mation in all the specimens. The specimens were then brought
back up to room temperature over another period of 4 h. To
remove any potential thermal residual stress all the specimens
were then subjected to a post-process temper. The specimens
were then heated to 170 1C over a period of 2 h. This tem-
perature was held for another 2 h and then was allowed to
return to room temperature, again over a period of 2 h.
Five different test lengths were conducted; 4500 impacts,
9000 impacts, 18 000 impacts, 36 000 impacts, and 72 000
impacts. Each test was performed with a new specimen and a
new striker and was repeated. The specimens and strikers were
cleaned in ethanol prior to testing.
All specimens were examined with a microscope, photo-
graphed and measured with a profilometer before and after
testing. The total wear was assessed by geometry change due to
the very small fraction of the overall specimen mass being
removed. Geometry change is also preferred as mass that can
be ‘moved’ via plastic deformation to a position where it can
bear little or no load and this is a phenomenon that is
undetected by mass difference techniques. Wear scar volumes
were estimated by modeling the wear scars as spherical caps
and using the recorded scar geometry to calculate an estimated
wear scar volume. The form and nature of any visible wear
debris was also recorded along with any notable features.
2.15.2.6.1.4 Results
2.15.2.6.1.4.1 Specimen overview and wear scar morphology
2.15.2.6.1.4.1.1 Untreated specimens
The wear scars can be easily seen by the naked eye as roughly
circular craters on the surface of the specimens and the wear
debris visible varied in size and nature. In general, the wear
438 Cryogenic Treatment of Engineering Materials
debris visible on the low carbon steel specimens can be char-
acterized as small amounts of fine dark colored debris with
more metallic particles visible after the longer tests and for the
lamellar graphite cast iron large metallic flakes were visible. In
all cases a negligible amount of debris was adhered to the ball.
Each wear scar was examined under a microscope and any
observations regarding the condition and form of the edge and
nearby debris were also recorded. In general, the low carbon
steel wear scars (Figure 9) exhibited smooth, well-defined
edges, some scars were slightly oval in shape and there was
pitting of the scar surface indicating that there was material
removal. The lamellar graphite cast iron wear scars were
rougher, but still had well-defined edges. The scars were gen-
erally regular in shape with some evidence of cracking around
the scar edge as shown in Figure 10.
2.15.2.6.1.4.1.2 Cryogenically processed specimens
The low carbon steel specimens had very little visible wear
debris, even after the longer tests; whereas there were small
amounts of dark, and after the longer tests more metallic
looking, debris on the untreated specimens. Again, in all cases
a negligible amount of debris was adhered to the ball. The
wear scar edge present after the 4500 impact test was very
Figure 9 Section of wear scar edge of a low carbon steel specimen
subjected to 72 000 impacts.
Figure 10 Section of wear scar edge of a lamellar graphite cast iron
specimen subjected to 72 000 impacts.
clean and well defined. Longer tests had slightly rougher,
cracked edges, but otherwise clean and well-defined wear scar
(Figures 11 and 12). All the wear scars created had grinding
marks (from the surface preparation) clearly visible in the wear
scar crater, the number of marks observed to be inversely
proportional to test length, indicating a mixture of brittle
fracture, and plastic deformation in the impact zone.
After the 4500, 9000, and 18 000 impact tests the cryo-
genically treated lamellar graphite cast iron specimens all had
clearly visible wear scars with grinding marks still distin-
guishable in the crater too. Each specimen had fine, dark
colored ring of wear debris around the edge of the wear scar
crater. The specimens subjected to 36 000 and 72 000 impacts
had thicker rings of wear debris (Figures 13 and 14) and in
the case of the 72 000 impact test some of the wear debris
were several millimeters away from the impact zone. The
predominant feature of the untreated lamellar graphite cast
iron was rough, but still well-defined wear scar edges with
some evidence of cracking (Figure 10). The wear scars created
on the untreated specimens also did not leave any evidence
of grinding marks in the wear scar craters. The grinding marks
Figure 11 Wear scar on a cryogenically processed low carbon steel
specimen subjected to 72 000 impacts.
Figure 12 Wear scar edge on a cryogenically processed low carbon
steel specimen subjected to 72 000 impacts.

Figure 13 Wear scar from a cryogenically processed lamellar
graphite cast iron specimen subjected to 72 000 impacts.
Figure 14 Wear scar edge from a cryogenically processed lamellar
graphite cast iron specimen subjected to 72 000 impacts.
Figure 15 Average wear scar diameter vs. number of impacts for cryogenically processed and untreated low carbon steel and lamellar graphite
cast iron specimens.
Cryogenic Treatment of Engineering Materials 439
visible on the processed specimens after testing (Figures 9
and 10) are wider or flatter indicating plastic deformation.
These differences suggest that the cryogenic processing has
modified the material properties so that plastic deformation
‘wear’ is the predominant wear mechanism rather than brittle
fracture as was the case with the untreated specimens. The
suggestion that the material has been modified is supported by
the difference in wear debris that was visible. The untreated
specimens produced large metallic flake-like debris whereas
cryogenically processed specimens produced much finer darker
particles.
2.15.2.6.1.4.1.3 Wear scar measurement
A profilometer was used to confirm the optically measured
wear scar diameters and to investigate the nature of wear scar
‘shoulders.’ Traces were taken across the center of each wear
scar and the typical profiles for each of the specimen types after
the 72 000 impact tests are shown here.
Three different diametric measurements were taken across
the center of the wear scar and the averages of these are shown
in Figure 15. The maximum and minimum measured values
are indicated by the error bars. Figure 15 clearly shows that the
cryogenic processing improves the impact wear resistance of
the low carbon steel specimens. For all test lengths the average
wear scar diameter of the cryogenically processed specimens is
between 55 and 80% that of the corresponding test for an
untreated specimen. The results of the lamellar graphite cast
iron are less clear cut. It is clear that for the longer tests the
cryogenic processing has improved the impact wear resistance
of the specimens to a similar extent to that of the low carbon
steel. That said, however, for the shorter tests it appears that
when considering the wear scar diameter, the cryogenic pro-
cessing has reduced the ability of the material to resist
impact wear.
The profiles shown in Figure 16 show that the size of the
wear scars on the cryogenically processed low carbon steel
specimens is clearly smaller, in depth and diameter, than the
440 Cryogenic Treatment of Engineering Materials

scar present on the untreated low carbon steel specimens for the
same number of impacts. As mentioned previously, the
untreated low carbon steel specimens exhibited plastically
deformed shoulders and this phenomenon is also present in the
cryogenically processed specimens. It is interesting to note that
the size of the shoulders has not decreased to the same degree as
the overall size of the wear scar. This suggests that the cryogenic
processing has not reduced the ductility of the material at the
expense of improving the wear resistance. That said however,
the level of surface cracking around the wear scar edges
has increased on the processed specimens (compare Figure 9
with Figure 12) suggesting that the ductility has actually been
reduced as the load on the material has exceeded the
plastic limit.
Figure 17 shows the difference in wear scar profile between
the untreated and cryogenically processed lamellar graphite
cast iron specimens subjected to 72 000 impacts. As with the
low carbon steel specimens the wear scar is smaller after pro-
cessing. The difference in wear scar depth is less than before,
but the plastically deformed shoulders are minimal on
the cryogenically processed specimens. This suggests that the
processing modifies the cast iron in such a way to reduce the
ductility of the material. Comparing the images of the wear
scar edges supports this statement as the surface cracking
visible on the untreated material (Figure 10) is not visible on
the edges of the processed cast iron (Figure 14).
2.15.2.6.1.4.1.4 Estimation of wear scar volume
Using the wear scar profilometry data an estimation of wear
scar volume can be made using the spherical cap method
(Figure 18). Again, the overall trend is that of the results pre-
sented so far in this section in that the processed materials

Figure 16 Profiles of wear scar on untreated and cryogenically processed low carbon steel specimens after 72 000 impacts.

Figure 17 Profiles of wear scars on untreated and cryogenically processed lamellar graphite cast iron specimens after 72 000 impacts.

exhibit improved resistance to impact. The cast iron has the
greatest change in wear volume between the untreated and
treated specimens. Given the magnitude of measured error for
these particular results it seems likely that there is a micro-
structural reason for this rather than simply experimental
variance, however a detailed microstructural analysis would
need to be performed.
2.15.2.6.1.4.1.5 Comparison with a ‘traditional’ heat treatment
process
Figure 19 compares the estimated wear scar volumes for the
lamellar graphite cast iron specimens presented here with
those estimated during work on laser hardening of lamellar
graphite cast iron.19 For clarity, only the results for the 72 000
impact tests are included. As part of that investigation,
Figure 18 Average wear scar volume vs. number of impacts.
Figure 19 Comparison of wear scar volume for lamellar graphite cast iron specimens subjected to 72 000 impacts.
Cryogenic Treatment of Engineering Materials 441
lamellar graphite cast iron specimens were subjected to laser
transformation hardening in an attempt to improve their
resistance to impact wear. Several different sets of laser
operating parameters, primarily energy density and speed,
were used when treating the cast iron specimens and these
induced different levels of localized phase transformations in
the surface of the material. These specimens were then sub-
jected to identical tests as those described earlier. The best
performing laser treated cast iron specimens exhibited
similar levels of wear to the best performing cryogenically
processed cast iron specimens tested for the work presented
here. It appears that the potential of improving the
wear resistance of lamellar graphite cast iron is similar to that
of more classical heat treatment in the form of the laser
hardening process.
442 Cryogenic Treatment of Engineering Materials
2.15.2.6.1.5 Summary
This case study shows that cryogenic processing can have a
positive effect on the wear resistance of Fe–C alloys. It also
demonstrates how relatively similar materials respond differently
to the same treatment. The low carbon steel that was tested using
the impact wear test rig showed some improvement to its ability
to resist impact wear but more investigation would be required to
confidently say if the improvement was ‘significant’ as described
in the literature.1 The lamellar graphite iron also showed
improvement in its ability to resist impact wear and the general
level of improvement was greater than the low carbon steel.
In general, the wear mechanisms observed in all specimens
were as typically found in impact wear studies. Where there is a
high impact velocity, which is considered to be the case
throughout this work, and therefore high impact energy, if there
is a soft material in the contact plastic deformation occurs with
ductile extrusion away from the contact. This was observed
particularly in the untreated specimens subjected to 72 000
impacts and, as can be seen in Figure 16, the low carbon steel
specimen exhibits large shoulders as a result of the plastic
deformation. The ‘softer’ material, the steel (Figure 9), exhibited
smooth wear scar edges that further support the presence of this
wear mechanism.
This case study also illustrates one of the difficulties of
assessing cryogenically treated materials as it is clear that much
more data would need to be collected to have a high level of
confidence in the performance improvements seen and their
subsequent repeatability. This would reveal any unknown
artefacts of the test procedure, such as changes in the loading
conditions, even though the measured variance is small.
Similarly, small microstructural flaws in the material, coin-
cident to the loading of those particular specimens, could
suddenly accelerate the wear process.
2.15.2.6.2 Sliding wear resistance of pearlitic brake disk
materials
2.15.2.6.2.1 Introduction
This case study reviews investigations concerning the influence
of cryogenic treatments on the sliding wear resistance of hypo-
eutectoid pearlitic carbon steel and lamellar graphite pearlitic
cast iron brake disk materials.35,40,57 These have been selected
because, although they are commonly commercially cryo-
treated components, there is almost no coverage of them in
the scientific literature. As anecdotal commercial evidence
suggests cryogenic treatments may substantially increase the
life of these components, preliminary tribological studies and
microstructural observations were conducted in an attempt to
provide some scientific verification.
2.15.2.6.2.2 Requirements of brake rotor materials
Brake rotors are invariably required to withstand a range of
conditions, which are strongly influenced by their specific
Table 16 Nominal compositions of brake disk materials studied
%wt. C Si Mn
SAE J431 G10 3.35–3.60 1.90–2.30 0.60–0.90
C50R 0.47 0.18 0.75
applications. In light goods vehicles (LGVs), sports cars,
whether used for motor racing, locomotives, or aircraft, brake
rotors need to provide consistent performance throughout
their design life. Composites and light alloys offer a range of
benefits including weight saving and therefore reduced fuel
consumption,60 high performance at extreme loads and tem-
peratures,61 as well as improved thermal stability.62
Nonetheless, traditional materials such as-cast irons and
plain carbon steels still dominate markets in terms of volume
produced, due to their low cost, ease of manufacture and good
machinability, as well as a high heat capacity which lends itself
to thermal stability. These factors are crucial as brake disks
must absorb the vast majority of the kinetic energy of the
vehicle during braking, much of which is inevitably converted
to heat. Even in typical LGV applications, brake disk tem-
peratures may reach 700 1C.63
Furthermore, the parameters of braking cycles vary sig-
nificantly. Typical LGV brake rotors may be subjected to longer
applications of low braking forces (to gently slow and stop the
vehicle) while racing cars will exert very high braking loads for
short periods of time on their braking systems. Temperature
requirements for motorsports brake rotor materials are there-
fore substantially higher, hence the wide use of ceramics and
composites. Conversely, brake rotors for domestic vehicles are
expected to have long fatigue lives (often as long as the life of
the whole vehicle); therefore steels and cast irons are still
desirable.
2.15.2.6.2.3 Experimental details
The commercial brake disk materials selected for this study
were SAE J431 G10 (a lamellar graphite cast iron) and AISI
1050/EN10083 C50R (a medium carbon steel). Material
compositions are given in Table 16.
The brake disk materials were tested as finished rotors
(with modifications made away from the wear track to fit
them to the test rig). Their surfaces had a machined finish
with a roughness of around 2.5 mm. Both materials had
pearlitic–ferritic microstructures while SAE J431 G10 also
contained lamellar graphite flakes and sulfide inclusions.
All specimens were subjected to the same deep cryogenic
treatment cycle, illustrated in Figure 20 and summarized as:
cooling at 1–2 K min
1 to 93 K, soaking for 24 h, heating at
1–2 K min
1 back to ambient temperature with a low-
temperature stress relief cycle conducted at 60 1C for 1 h.
The testing program involved Vickers macro- and micro-
hardness tests (20 kgf/196.2 N and 0.05 kgf/4.905 N, respec-
tively), pin-on-disk sliding wear testing using a Plint TE99
(BICERI/Eyre) Universal Wear Testing Machine (Figure 21)
15 mm diameter hardened AISI 52100 chrome steel balls
(Table 17), volume-loss wear measurements using measure-
ments made with a 2D stylus profilometer (Figure 22) and
subsurface microstructural observations using optical and
P S Cr Mo Ni
0.10 0.15 – – –
0.010 0.007 0.03 o0.01 0.03

Figure 20 Deep cryogenic treatment cycle applied to specimens
used in this study.
Figure 21 TE99 in pin-on-disk mode as used in this study.
Table 17 Properties of AISI 52100 chrome steel wear pins
Material HV98.1N (MPa) Ra,max (μm) Diameter (mm)
AISI 52100 6878–8829 0.125 15
scanning electron microscopy. Given the changes subsequently
reported for the pearlitic carbon steel, additional samples were
later prepared for transmission electron microscopy.
Sliding wear tests were conducted over a range of initial
Hertzian contact pressures and sliding speeds in each case. As
it is difficult to replicate realistic brake cycling conditions in a
laboratory environment, these were chosen to provide com-
parative data when a dominant wear mechanism could be
clearly defined. In the case of SAE J431 G10 GCI brake rotors,
this involved contact pressures of 375.0, 562.5, and 750.0 MPa
and sliding speeds of 1.34, 1.78, and 2.24 m s
1. Similarly,
C50R carbon steel rotors were subjected to contact pressures of
1000, 1300, and 1600 MPa at a fixed sliding speed of
Cryogenic Treatment of Engineering Materials 443
1.18 m s
1. Optical and scanning electron micrographs were
generated from untreated and cryotreated brake rotors not
used in testing, to ensure that the observed microstructures
were not affected by thermal or mechanical conditions
resulting from wear testing.
2.15.2.6.2.4 Results
2.15.2.6.2.4.1 Hardness
While neither the bulk hardness (Table 18) or matrix hardness
(Table 19) of the gray cast iron (G10) material was sub-
stantially affected by the cryogenic treatments, the carbon steel
(C50R) was shown to respond significantly, with 28 and 17%
increases in hardness determined during macro- and micro-
hardness testing respectively.
2.15.2.6.2.4.2 Wear testing
Similarly to the hardness results, wear tests of the G10 and
C50R brake rotors displayed very different results. In the case
of the GCI rotors, the changes in measured wear rates fol-
lowing cryogenic treatment were highly variable (Figure 23)
with a weak trend toward increasing benefits of cryogenic
treatments in improving wear resistance under higher contact
pressures. When changes in wear rates were considered against
overall sliding distance (Figure 24) another weak trend with an
apparent negative correlation between increased wear resis-
tance and longer sliding distances. Optical microscopy of wear
scars revealed no dominant change in wear mechanism from
predominantly abrasion and pitting.
By contrast, sliding wear testing of the carbon steel brake
rotors showed a consistent, if statistically small, increase in
wear resistance following deep cryogenic treatment over all the
contact conditions tested (Figure 25). The mean reductions in
wear rate at initial contact pressures of 1000, 1300, and
1600 MPa were 14.4, 12.1, and 22.7%, respectively. However,
observations of the worn surfaces (Figure 26) revealed no
substantial change in the dominant wear mechanism that was,
once again, abrasion and pitting.
2.15.2.6.2.4.3 Microstructural observations
In neither case did optical microscopy reveal any obvious
changes in microstructure that may explain the observed
changes in mechanical performance of either material. Darkfield
optical micrographs (Figure 27) revealed a mixture of coarse (A)
and fine (B) pearlite was the dominant structure in G10 speci-
mens, along with lamellar graphite flakes (C) and manganese
sulfide inclusions (small bright spots). In C50R specimens
(Figure 28) the microstructure again consisted of coarse (A) and
fine (B) pearlite interspersed with a smaller number of ferrite
grains (C). Scanning electron microscopy allowed these struc-
tures to be resolved further, but again did not reveal any
obvious microstructural changes due to CT processes.
Given the consistent changes measured in its hardness and
wear resistance, the microstructural characterization was con-
tinued for the carbon steel (C50R) using transmission electron
microscopy to obtain evidence for any change in nano-
precipitation behavior or dislocation structure that may have
occurred due to deep cryogenic treatment. The micrographs
generated (Figure 29) revealed similar nano-precipitates in
both untreated and cryotreated samples. These ranged from
50–150 nm hexagonal, to 10–50 nm spherical and tiny
444 Cryogenic Treatment of Engineering Materials

Figure 22 Typical profilometry traces of wear scars used to estimate wear volume in brake disk specimens.

Table 18 Macro-hardness test results from brake disk surfaces

Specimen Treatment HV196.2N (MPa) Coefficient

type of variation

SAE J431 G10 As-received 2070 3.5%

DCT 2109 ( þ 1.9%) 4.9%
C50R As-received 1622 4.3%
DCT 2071 ( þ 27.7%) 1.8%

Table 19 Micro-hardness test results from brake disk samples

Specimen Treatment HV0.4905N (MPa) Coefficient

type of variation

SAE J431 G10 As-received 3600 17.2% Figure 24 Change in wear rates from G10 pin-on-disk tests
DCT 3679 ( þ 2.2%) 11.8% normalized by contact pressure and sliding speed.
C50R As-received 1927 2.6%
DCT 2244 ( þ 16.5%) 2.0%
(o10 nm) rod-like precipitates. Observations made along
phase interfaces revealed no evidence of change although,
qualitatively, there did appear to be fewer dislocations in the
cryogenically treated samples.

2.15.2.6.2.5 Summary
This case study illustrates that cryogenic processing can have a
significant positive effect on the wear resistance of pearlitic
carbon steels, although its influence over lamellar graphite cast
irons remains unclear. It also demonstrates the innate diffi-
culty in identifying the fundamental microstructural changes
that are responsible, given the need for nanoscopic investiga-
tions that are beyond the reach of most providers or users of
cryogenic treatment processes. It is also challenging to make
representative observations of microstructures on the basis of
commercial components, where geometric factors may influ-
Figure 23 Change in wear rates determined from G10 pin-on- ence the homogeneity of the structure produced in different
disk tests. regions during manufacturing.

In the case of the cast iron, the differential between rates of
thermal contraction of the graphite flakes and adjacent phases
may have resulted in damaging stresses being exerted. This, in
turn, may have reduced the self-lubricating properties of GCI64
that are dependent on the shearing of graphite flakes along
precise crystallographic planes.65
The increases in hardness (415%) and wear resistance
(415%) for the pearlitic carbon steel tested are significant and
support the need for further study, as there are other micro-
structural changes that remain to be explored. For instance
nano-precipitates may have been obscured, in the present study,
along grain boundaries or at phase interfaces, while changes in
Figure 25 Volumetric wear rates (71s) determined from carbon
steel brake pin-on-disk tests.
Figure 26 Typical wear scars developed in (top) standard treated and (bottom) cryotreated C50R disks.
Cryogenic Treatment of Engineering Materials 445
the distribution of dislocations throughout the material may
significantly influence its mechanical performance.
2.15.3 Cryogenic Processing of Nonferrous Alloys
Considering the wide use of nonferrous metals, particularly in
structural applications and machine tools, there is a dis-
proportionate focus on ferrous-based alloys as the target of
cryogenic processing research and commercial endeavor. This is
probably because much of the early research in this area was
driven by tool manufacturers requiring greater wear resistance
and the oft-reported ‘fact’ that cryogenic processing relies on
converting the any retained austenite into martensite. That said,
light alloys such those based on aluminum, titanium, and
magnesium, represent a developing area for cryogenic treatment
with a view to minimize the trade-offs that are made in per-
formance at the expense of mass reduction. A much smaller area
of focus considers whether cryogenic treatment has potential to
be applied to nonmetallic composite materials.
This section identifies the state of the art and trends in
performance modification that can typically be achieved by
subjecting nonferrous metals to cryogenic processing and then
offers a selection of specific examples of its use across the main
light alloy families and cobalt-bonded tungsten carbide.
2.15.3.1 State of the Art
When compared to the volume of work conducted to inves-
tigate the cryogenic treatments on ferrous materials, the body
of work investigating its effect on nonferrous materials is very
446 Cryogenic Treatment of Engineering Materials
Figure 27 Optical micrographs of non-cryotreated (top) and
cryotreated (bottom) SAE J431 G10 material.
small. Much of the effort has been focused on the performance
of these classes of materials when used in components that
typically operate at cryogenic temperatures (e.g., in space) or
their response to being subjected to a manufacturing process
that has a cryogenic element to it (e.g., cryogenic machining,
rolling, or friction stir welding) rather than a cryogenic treat-
ment process as defined here. The varied but preliminary
studies conducted to date clearly demonstrate the need for
greater investigations into the effects of cryogenic treatments in
light alloys.
The broad approach to investigating the behavior of these
materials is similar to that used for ferrous materials; speci-
mens are subjected to a fixed CT process followed by a range of
mechanical tests and microstructural analyses.
In the same way that there are common microstructural
changes caused by cryogenic treatment to be found across fer-
rous materials the same is true for nonferrous metals and this is
most often described as taking the form of a microstructural
refinement of some description. For example, in titanium alloys
it appears that cryogenic treatment changes the morphology of
b particles which means the now coarse divorced eutectic b
phase particles penetrate the matrix and thus strengthen it
against crack propagation. Broad observations described as
‘refinement of grain size’ and ‘microstructural stabilization’ are
Figure 28 Optical micrographs of non-cryotreated (top) and
cryotreated (bottom) C50R material.
also regularly made for many light metal alloys but without
conclusive evidence being presented.
These microstructural changes are often presented in
attempts to explain changes in the performance of materials
subjected to cryogenic treatment that result from common
engineering assessments. It is often suggested that the bulk
macro-hardness of the material changes and that this is
dependent on the parameters of the treatment process, usually
the length of the soak at a particular cryogenic temperature. If
this is optimized then some materials show potential for an
improvement in their hardness, but this is often restricted to an
‘apparent hardness increase’ reported by users of a treated
component rather than a robust laboratory analysis.
Improvement in hardness is often an area of interest
because of its role in wear performance. As with ferrous metals,
for nonferrous materials to be subjected to contacts across a
range of loads and lubrication regimes is an increasingly
common occurrence, particularly as component lightweighting
becomes more prevalent in the automotive and aerospace
industries. The largest gains to date have been seen in mag-
nesium alloys but the process has competition in this area in
the form of the much more mature coating technologies.
Although the bulk of work carried out to investigate cryogenic
processing of nonferrous metals has considered alloys of

Figure 29 TE micrographs showing: (a) non-cryotreated and (b) cryotreated nano-precipitates in ferrite; (c) non-cryotreated and (d) cryotreated
ferrite–ferrite grain boundaries.
aluminum, titanium, and magnesium some consideration has
been given to other nonferrous alloys. These studies tend to
consider the response of one particular parameter of one
particular alloy so therefore it is very difficult to draw any
cross-cutting conclusions. Examples of these studies include;
the improvement of the thermal conductivity of a proprietary
copper alloy66 and improving electrical discharge machining
(EDM) by treating the electrodes.67 An emerging area is the
consideration of cryogenic processing as a suitable treatment
for composite materials, particularly those with a metallic
component such as metal–matrix–composites (MMCs).68
Although a niche area of work, cryogenic processing has
also been shown to have beneficial effects on nonmetallic
composite materials, such as the PTFE/Kevlar hybrid fabric.7
Typically used as bearing liner materials due to their tribolo-
gical properties, PTFE and Kevlar exhibit poor adhesion to the
resin binder due to their chemically inert nature. Cryogenic
treatment was shown to improve the wear resistance of the
hybrid material, with the improvement suggested to be as a
Cryogenic Treatment of Engineering Materials 447
result of increased mechanical interlocking of the phenolic
resin used, as a result of the fabric roughening at cryogenic
temperatures.
2.15.3.2 Aluminum Alloys
As the oft-cited mechanisms behind cryogenic processing are
similar to those behind ageing, it seems likely that aluminum
alloys that are age-hardenable should also respond to cryogenic
processing. Work conducted with a view to investigating this
hypothesis on AA6061 discovered that adding a deep cryogenic
soak (optimized to be in the range 18–21 h) in between a
quenching and ageing treatment had an effect on its perfor-
mance.69 When compared to AA6061-T6 the cryogenically
processed material had up to three times the hardness and when
subjected to a simple milling process showed an improvement
in roughness (1.4Ra–0.7Ra). Both of these effects are attributed
to the formation of fine precipitates during the cryogenic
448 Cryogenic Treatment of Engineering Materials
processing. Similarly, AA 6106-T4 subjected to DCT and
micro-abrasion tests demonstrated a 26% reduction in wear
rate.70
Efforts to improve the resistance of aluminum alloys to
crack growth, either through fracture or fatigue, have led to
attempts to apply cryogenic treatment to these types of
materials. A 7075-T651 alloy was cryogenically treated at

196 1C (77 K) caused a 12% increase in the Charpy impact
energy, but without any significant change in strength or
hardness. It is interesting to note that specimens held at their
soak temperature for 2 h showed no significant improvement,
whilst those treated for 48 h did, indicating a time-dependent
microstructural change is likely responsible.71
Research attempting to improve the wear resistance of alu-
minum overhead conductor suspension clamps recorded a 20%
increase in the lifespan of the conductor wire material along
with a reduction in damage to the suspension clamps. This was
judged to have occurred as a result of an increase in ‘ultra-fine
distributed precipitates’ following cryogenic treatment.72
This effect and the inhibiting effect of increased dislocations
following cryogenic treatment are discussed by Wang et al.73 in
their study on the effects of cryogenic pretreatments on the
mechanical performance of friction-stir-welded joints in 2024-
T351 aluminum alloy. In testing, they observed improved
elongation before fracture in samples having undergone cryo-
genic treatment.
2.15.3.3 Magnesium Alloys
The recent trend for lightweighting engineering components in
the aerospace and automotive sectors has seen a significant
increase in the use of magnesium alloys because of their low
relative density. In automotive components, where it is bene-
ficial to reduce rotating/moving mass, there are many sliding
contacts where wear resistance is critical. As one of the gen-
erally cited benefits of CT is to improve wear resistance, it
seems worthwhile to attempt to apply it to magnesium alloys.
Similarly, although many magnesium alloys have adequate
creep resistance at ambient temperatures, their limitations are
quickly reached at the elevated temperatures found in auto-
motive powertrain components. As one might expect with its
near universal use when a magnesium alloy is specified AZ91,
particularly because of its castability, is commonly used as the
material to be treated.
Studies investigating the effects of cryogenic treatment on
AZ91 magnesium alloy have observed improved wear resis-
tance after DCT at
196 1C (77 K).74 A 460% reduction in
wear rate of an Mg–Zn–Gd alloy following deep cryogenic
treatment by direct immersion in LN2 have also been achieved.
Following treatment, the alloy was observed to contain a
substantially greater volume fraction of secondary phase par-
ticles, to which the increase in wear resistance was attributed,
and it had changed from a disordered solid solution to an
ordered solid solution.75
Efforts to improve the creep resistance of AZ91 magnesium
alloy by using a cryogenic treatment have resulted in improved
wear resistance after DCT at
196 1C (77 K).74 The improved
creep behavior was attributed to morphological changes which
prevented grain boundary sliding at high temperatures.
Tests to determine the tensile properties of an extruded
Mg–Gd–Y–Zr(Mn) alloy at cryogenic temperatures have
shown a significant increase in tensile strength, yield strength,
and elongation before fracture, which is attributed to the
precipitation of a large number of ‘rod-like, tree-like, and
chrysanthemum-like’ features within the microstructure. While
direct immersion in LN2, or CQ may lead to thermal shock
and brittleness of materials, these investigations seem to show
that the microstructural changes due to DCT may have a more
significant effect on the performance of a material.76
It appears that there is at least some degree of con-
sensus about the mechanism behind observable mechanical
improvements that can be made to magnesium alloys using
cryogenic processing.
Tests on AZ31 magnesium alloy77 subjected to range of
DCT soak times (2–48 h) using electron microscopy techni-
ques and pole figure analysis suggest that cryogenic processing
causes changes in grain orientation. This change is attributed
to a frame-like twinning process and results in a reported
increase in hardness and tensile strength but this improvement
is highly dependent on the length of the soak. This means that
any specific application would need optimizing to ensure
repeatable results.
Similar work on AZ31, and also ZK60, shows that there are
changes to the grain orientation accompanied by second phase
precipitate strengthening78 again resulting in reported
improvements in hardness and tensile strength. A more
quantitative analysis79 adds to these findings by stating that
for AZ91 the sizes of the precipitates are refined from 8–10 mm
to 2–4 mm. It has also been suggested that, in the case of AZ91
in particular, the improvement in hardness is facilitated
by the aluminum atoms jumping to defect sites as the
material contracts at low temperature80 and then forming the
basis for nucleation of precipitates during the final aging
process.
2.15.3.4 Titanium Alloys
There is very little known about the effect that cryogenic pro-
cessing has on titanium and its alloys. This is due to the
general understanding that cryogenic processing is a ‘heat’
treatment and that commercially available titanium alloys are
not amenable to thermal hardening. Some research has
attempted to investigate the effect of CT on titanium alloys but
the results are inconclusive and are often arrived at obliquely
during research not directly considering the problem.
In dentistry, nickel–titanium alloys are commonly used as
an alternative material to stainless steel for endodontic tools
which are used to remove material during root canal therapy.
CT of these types of instruments results in a small increase in
measureable micro-hardness, but no apparent ‘hardness’
improvement when used clinically,81 or in their wear
resistance.82
What can be broadly described as ‘materials at low tem-
perature’ research, such as conducted by the space community,
often produces insight that crosses over into cryogenic pro-
cessing. Mechanical tests performed on a Ti–2.5Cu alloy
immersed in LN2 at temperatures of 77 K found that that both
the ductility and low-cycle fatigue life of the alloy was
improved.83 It was concluded that nano-scale precipitates
 Cryogenic Treatment of Engineering Materials 449

hinder the movement of dislocations, thereby preventing crack
formation.
Commercial alloy grades of titanium, such as Ti–6Al–4V,
are commonly used in components where they are subjected
to tensile loads. CT has been used to modify the plasticity of
Ti–6Al–4V and, when combined with a suitable ageing pro-
cess, this can be improved by 420% with no change in micro-
hardness but at the expense of some (5%) reduction in tensile
strength. It is suggested that this improvement is due to the CT
reducing the b phase content of the material thus decreasing
the resistance to dislocation movement. The combination of
CTs and aging treatments appears to cause the formation and
interaction of dislocation networks, resulting in the formation
of twins within the microstructure.84
Due to their low shear modulus, titanium alloys regularly
undergo surface engineering (usually a deposition-type coat-
ing) when they are subjected to sliding contacts. Cryogenic
processing has potential to be used in lieu of a coating for
these applications and it has been reported that DTC can
produce a slight increase in hardness, due to grain refinement,
giving improved resistance to sliding wear. It has also been
reported that the increase in hardness is linear with soak
temperature and soaking time.85
Due to their reputation as ‘difficult to machine’ materials
titanium alloys have been the focus of a significant proportion
of the development of cryogenic machining. There has been a
considerably less effort expended investigating the potential of
cryogenically processing the material prior to processing using
conventional machining techniques (i.e., non-cryogenic
machining).
Due to its high electrical resistivity, titanium is difficult to
process using EDM techniques. Many avenues (such as ultra-
sound assisted EDM, dry EDM, and indeed cryogenically
cooling the electrode) have been explored to improve the
efficiency of EDM for titanium alloys, including cryogenically
processing the workpiece prior to machining operations being
performed. A 24 h DCT soak has been found86 to improve the
machinability of Ti 6246 by allowing up to 8.5% improve-
ment in material removal rate in an EDM drilling operation.
Claims for EDM operations using proprietary titanium alloys
producing greater improvements have also been made.87
The wear rate of the tool is also a significant consideration
in EDM processes and this was reduced by around 30%. The
surface roughness measured inside the holes improved by up
to 10%. It is suggested that these improvements are as a result
of the reduction in electrical resistivity and conductivity (as
measured using a standard four probe setup) but it is
unknown how the cryogenic processing causes this change in a
titanium alloy.86
2.15.3.5 Cobalt-Bonded Tungsten Carbides
In the last decade, attention has partly shifted from the
application of cryogenic treatments to tool steels, to its
application to sintered, cobalt-bonded tungsten carbide tool
materials. These materials (often referred to as ‘hardmetals’ or
‘cermets’) are inherently harder and more wear resistant, with
greater thermal stability, and are therefore commonly used
for high volume manufacturing operations. When combined
with appropriate coatings they can sometimes be used in
high-speed machining and hard machining operations as
well.
Although very minimal work has been done to characterize
the mechanical properties of cryogenically treated sintered
carbides to date, alongside a variety of tool wear and tool-life
studies the hardness of these materials has been reported.
Summarized in Table 20, it can be seen that the hardness
changes reported are far more moderate than those reported
for tool steels. However, these data suggest that cryogenic
treatments may significantly improve the hot hardness88 of

Table 20 Hardness data reported for cryotreated WC–Co

Investigators Material description Temperature (1C) Treatment Hardness (change)

Seah et al.90 WC–7Co–1?? Ambient As-received 89.3 HRA

Cryoquenched 89,4 ( þ 0.1%)
Cryotreated 89.4 ( þ 0.1%)
Cryo þ Temper 89.4 ( þ 0.1%)
Cold treated 89.5 ( þ 0.2%)
Cold þ Temper 89.7 ( þ 0.4%)
Thakur et al.91 93WC–Co–?? Ambient Untreated 17760 HV19.6
Cryotreated 17850 ( þ 0.6%)
SreeramaReddy et al.88 Kennametal P-30 Ambient Untreated / cryotreated 88.5 / 86.5 HRA (
2.2%)
WC–17Co–1.4TiC–1.4TaC 100 85.0 / 86.0 ( þ 1.2%)
200 82.0 / 84.0 ( þ 2.4%)
Multilayer CVD coating: 300 81.0 / 83.0 ( þ 2.5%)
TiN: 1.5 mm, TiCN: 12.5 mm, 400 76.5 / 79.8 ( þ 4.3%)
Al2O3: 6 mm, TiN: 5 mm 500 73.0 / 78.0 ( þ 6.8%)
600 63.0 / 71.8 ( þ 14.0%)
Gill et al.89 ISO-P25 Ambient Untreated 88.2 HRA
WC–6Co–1.4TiC SCT 92.6 ( þ 5.0%)
DCT 92.8 ( þ 5.2%)
Thornton et al.92 SHM H13A Ambient Untreated 20740 HV4.905
WC–6Co DCT 22 640 ( þ 9.2%)

Note: ?? indicates the presence of unknown additional alloying elements.

450 Cryogenic Treatment of Engineering Materials

Table 21 Tool wear data reported for cryotreated WC–Co

Investigators Tool material Feed rate Depth of Cutting speed Tool-life changes
(mm rev
1) cut (mm) (m min
1) reported

Gill et al.94 Sandvik ISO P-25 0.1 1.0 110 þ 27–36%

SPUN 120308 130 þ 21–27%
WC–6Co–1.4TiC 150 þ 19–25%
180 þ 13–20%
Gill et al.94b Sandvik ISO P-25 0.1 1.0 110
3.9– þ 34%
SPUN 120308 130 þ 9.8–32%
WC–6Co–1.4TiC 150 þ 15–24%
TiAlN coated 180 þ 18–21%
SreeramaReddy et al.88 Kennametal ISO P-30 0.22 1.0
WC–17Co–1.4TiC–1.4TaC
200 þ 7.7%
Multilayer CVD coating: 250 þ 22%
iN: 1.5 mm 300 þ 22%
TiCN: 12.5 mm 350 þ 15%
Al2O3: 6 mm
TiN: 5 mm
Thornton et al.92 (Reduction SHM H13A 0.2 0.5 50 0%
in flank wear values given) WC–6Co 95 þ 6%
140
5%

complex WC–Co alloys, while only shallow cryogenic

treatments (163–193 K) may be required89 for this to happen.
Due to their prevalence as cutting tools, and the relative
difficulty with which laboratory samples can be made from
sintered carbide materials, the majority of studies to date have
focused on tool-life and tool wear. The results from these have
generally indicated benefits to the application of cryogenic
treatments, as summarized in Table 21. However, as might be
expected and supported by observations made by the present
authors,92 increases in hardness and predominantly abrasive
wear resistance is typically accompanied by a decrease in
toughness. In the case of cutting tools this may lead to more
unexpected catastrophic failures if the material properties are
not properly characterized and cutting parameters adjusted
accordingly.
Generally speaking, it has been reported that cryogenic
treatment diminishes the adhesion strength of common tool
coatings (such as TiN and (Ti, Al)N) resulting in an overall
decrease in tool-life,93 although cryogenic treatment has con-
sistently been found to improve the tool-life of uncoated
carbide tools.94 The reason for this weakening of the interface
between coating and substrate is thought likely to be due to
the difference in thermal contraction between the two mate-
rials during cryogenic treatment.
During cutting operations, tools are subjected to high
temperatures and therefore it is important that any changes as
a result of a heat treatment or coating process are stable at
those temperatures. A good indicator of this is the relative
performance of tools under dry and wet, continuous and Figure 30 Influence of cutting conditions on performance of
interrupted machining processes – the latter conditions lead- cryotreated WC–Co cutting tools57 based on studies by (a) Yong
ing to greater cooling and lower temperature rises in the tool et al.95 and (b) Gill et al.96
material.
Based on the studies of Yong et al.95 and Gill et al.96
(Figure 30), it appears as though at least some of the changes due to deep cryogenic treatment could be increased by 10%
resulting from cryogenic treatments are not thermodynamically when milling a medium carbon steel with coolant, as opposed
stable. Yong et al. reported that the improvement in tool-life to without. During turning operations, Gill et al. observed that

interrupting the cutting process (disengaging the tool from the
workpiece) was more effective in prolonging the life of cryo-
treated tungsten carbide inserts than by using coolant.
Numerous process factors influence the properties of
WC–Co materials, with the physical effects responsible tend-
ing to concern the concentration of cobalt binder or carbon
near the surface, compressive stresses induced in the WC phase
due to cobalt hardening, and the precipitation of fine eta-
phase carbides. Reported microstructural changes due to
cryogenic treatments are often not backed up by robust char-
acterization techniques and are sometimes contradictory. For
instance the shrinkage/densification of the cobalt binder,91
enlarging of the carbide grains88 and resulting in fine eta-phase
carbide precipitates88,90,97 have all been suggested to play
a role.
In a particular study of note, Gisip et al. performed a series
of energy-dispersive X-ray spectroscopic analyses at increasing
distances from the edges of flouted router bits used to machine
medium-density fiberboard. Their chemical analysis illustrated
a significant reduction in the rate of removal of binder phase
and carbide grains from the surface following cryogenic
treatment. There was also less tendency for high-temperature
oxidation and corrosion to occur.
The range of tool-life and tool wear studies available for
cobalt-bonded tungsten carbides paints a compelling picture
that cryogenic treatments can offer significant benefits. How-
ever, to date, the explanation from rigorous microstructural
studies are lacking, thus preventing more widespread adoption
of the technique.
Acknowledgments
The authors wish to acknowledge the assistance of Cryogenic
Treatment Services Ltd. (UK) (http://www.195below.co.uk/)
for carrying out the deep cryogenic treatment on the specimens
and the Materials Engineering Research Institute (MERI) at
Sheffield Hallam University (UK) (http://www.shu.ac.uk/
meri) for the use of their facilities to capture a number of the
wear scar images used in the case studies presented.
See also: 2.1 Fundamentals of Heat Treating Metals and Alloys
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Relevant Websites
http://www.195below.co.uk/
Cryogenic Treatment Services Ltd.
http://www2.le.ac.uk/departments/engineering/research/mechanics-of-materials
Mechanics of Materials Research Group, University of Leicester.
http://www.leonardocentre.co.uk/
The Leonardo Centre for Tribology, The University of Sheffield.