ABSTRACT

The use of cryogenic treatment (CT) to improve mechanical properties of materials has been developed
from the end of the Sixties. At the present time, the initial mistrust about CT has been cleared up and
many papers about different materials reporting laboratory tests results, microstructural investigations and
hypothesis on CT strengthening mechanisms have been published. The removal of retained austenite
combined with fine dispersed carbides precipitation has been widely observed and their effects on
mechanical properties have been measured. In addition, some recent studies have pointed out a different
mechanism for fatigue strengthening of stainless steels, which involves nano-martensite formation during
the CT. The present paper summarizes the state of art about CT, focusing on methods, parameters,
results and assumed microstructural mechanisms, in order to get a starting point for new researches to
come.






Contents
Abstract ....................................................................................................................................................................... iv
Contents ....................................................................................................................................................................... vi
List of tables ..............................................................................................................................................................viii
List of figures .............................................................................................................................................................. xi
1. Introduction ................................................................................................................................................... 1
1.1. Definition ....................................................................................................................................................... 1
1.2. Applications ................................................................................................................................................... 2
1.3. Advantage over Conventional Surface Coating ............................................................................................. 2
2. Cryogenic Heat Treatment Process ............................................................................................................... 5
2.1. Mechanism ..................................................................................................................................................... 5
2.2. Types of CT ................................................................................................................................................... 7
3. Treatment Parameters................................................................................................................................... 9
3.1. List of Parameters .......................................................................................................................................... 9
4. Cryogenic System ........................................................................................................................................ 13
4.1. Definition ..................................................................................................................................................... 13
4.2. Types of Cryogenic System ......................................................................................................................... 14
4.3. Direct Nebulization System ......................................................................................................................... 16
5. Effect on Microstructure of Tool Steel ........................................................................................................ 19
5.1. Effect on Ferrous Materials ......................................................................................................................... 20
5.2. Effect on Non-Ferrous Materials ................................................................................................................. 23
6. Effect on Mechanical Properties ................................................................................................................. 25
6.1. Reason Affects
Mechanical Properties ........... 25
6.2. Wear Resistance ...... 26
6.3. Hardness ................. 28
6.4. Fracture Toughness . 30
6.5. Tensile and Bending
Strength ................................. 31
7. Evaluation of Factors
influencing DCT ................... 33
8. Conclusions ............ 35
9. References ............. 37
10. List of Figures












INTRODUCTION
The word Cryogenics is derived from the Greek words 'Kryos" (meaning cold) and "Genes" (meaning born). The
cryogenic processing is modification of a material or component using cryogenic temperatures. Cryogenic temperatures
are defined by the Cryogenic Society of America as being temperatures below 120K (-244F, -153C). Cryogenic
processing makes changes to the crystal structure of materials. The major results of these changes are to enhance the
abrasion resistance and fatigue resistance of the materials.
The thermal treatment of metals must certainly be regarded as one of the most important developments of the industrial
age. One of the modern processes being used to treat metals (as well as other materials) is cryogenic tempering. Until
recently, cryogenic tempering was viewed as having little value, due to the often brittle nature of the finished product. It
is only since the development of computer modeled cooling and reheats curves that the true benefits of cryogenically
treated materials have become available to industry and the general public. Cryo tempering is a permanent, non-
destructive, non-damaging process (not a coating) which reduces abrasive wear (edge dulling), relieves internal stress,
minimizes the susceptibility to micro cracking due to shock forces, lengthens part life, and increases performance. Cryo
S.
No.
Title
1 Flow Process of Cryogenic Heat Treatment
2 Martensite Formation Temperatures for various % of Carbon content
steels
3 Temperature Profile in DCT
4 Sketch of Direct Nebulization Cryo-System
5 Variation of Wear Rate with Tempering Temperature
6 Variation of Vicker Hardness with Tempering Temperature
7 Variation of Rockwell Hardness with Tempering Temperature
8 Fatigue Life extensions of Fe-18Cr-8Ni Austenitic Steels
9 Variation of Wear Rate with Holding Time
treated pieces are also less susceptible to corrosion. The deep cryogenic tempering process is a one-time, permanent
treatment affecting the entire part, not just the surface.
In Ferrous metals, cryogenic processing converts retained austenite to martensite and promotes the precipitation of very
fine carbides. Fine carbon carbides and resultant tight lattice structures are precipitated from cryogenic treatment. These
particles are responsible for the exceptional wear characteristics imparted by the process, due to a denser molecular
structure; reducing friction, heat, and wear. Cryogenic Processing is not a coating. It affects the entire volume of the
material. It works synergistically with coatings. Furthermore, the cost of cryogenic treatment is said to be less than the
cost of coating, which is currently a popular method for improving tool life. Cryogenic Processing has a great effect on
High Speed Steel cutting tools. The normal result is that the tools will last considerably longer, typically 2 to 3 times
longer. Cryogenic processing establishes a very stable piece of metal that remains distortion free. The process will also
stabilize some plastics. The stamping, forming and cutting die industry is one of the first places where cryogenic
processing worked its wonders. Cryogenically treated metals form better. Valve spring life can be improved up to seven
times over the shot peened life by the use of cryogenics.












TYPICAL CRYOGENIC PROCESS

RAMP DOWN: Lowering the temperature of the object. A typical cryogenic cycle will bring the temperature of
the part down to -300F over a period of six to ten hours. This avoids thermally shocking the part. There is ample
reason for the slow ramp down. . Think in terms of dropping a cannon ball into a vat of liquid nitrogen. The
outside of the cannon ball wants to become the same temperature as the liquid nitrogen, which is near -323F.
The inside wants to remain at room temperature. This sets up a temperature gradient that is very steep in the first
moments of the parts exposure to the liquid nitrogen.

SOAK: Holding the temperature low. A typical soak segment will hold the temperature at 123K for some period
of time, typically eight to forty hours. During the soak segment of the process the temperature is maintained at
the low temperature. Although things are changing within the crystal structure of the metal at this temperature,
these changes are relatively slow and need time to occur. One of the changes is the precipitation of fine carbides.
In theory a perfect crystal lattice structure is in a lowest energy state. If atoms are too near other atoms or too far
from other atoms, or if there are vacancies in the structure or dislocations, the total energy in the structure is
higher. By keeping the part at a low temperature for a long period of time, we believe we are getting some of the
energy out of the lattice and making a more perfect and therefore stronger crystal structure

RAMP UP: Bringing the temperature back up to room temperature. A typical ramp up segment brings the
temperature back up to room temperature. This can typically take eight to twenty hours. The ramp up cycle is
very important to the process. Ramping up too fast can cause problems with the part being treated. Think in
terms of dropping an ice cube into a glass of warm water. The ice cube will crack. The same can happen.

TEMPER RAMP UP: Elevating the temperature to above ambient. A typical temper segment ramps the
temperature up to a predetermined level over a period of time. Tempering is important with ferrous metals. The
cryogenic temperature will convert almost all retained austenite in a part to martensite. This martensite will be
primary martensite, which will be brittle. It must be tempered back to reduce this brittleness. This is done by
using the same type of tempering process as is used in a quench and temper cycle in heat treat. We ramp up in
temperature to assure the temperature gradients within the part are kept low. Typically, tempering temperatures
are from 300F on up to 1100F, depending on the metal and the hardness of the metal.

TEMPER HOLD: Holding the elevated temperature for a specific time. The temper hold segment assures the
entire part has had the benefit of the tempering temperatures. A typical temper hold time is about 3 hours. This
time depends on the thickness and mass of the part. There may be more than one temper sequence for a given
part or metal. We have found that certain metals perform better if tempered several times.





Fatigue Resistance

Some studies about CT and fatigue have been conducted at the Precision and Intelligence Laboratory of
the Tokyo Institute of Technology [27-29]. During these researches the authors have measured the Ms
(martensite start temperature) of a stainless steel with the acoustic emission technique, then they have
cooled the samples just 3 K above Ms and they have returned the samples to the room temperature. In
[27] the test has been conducted on an austenitic Fe-18Cr-8Ni stainless steel pre-strained by 2% in order
to increase the dislocation density. The result, as reported in Fig. (3), have shown that the CT does not
increase the fatigue life in the low-cycle regime (< 104 cycles). However, CT samples have shown longer
life in high-cycle regime (> 104 cycles). Considering a maximum stress of 350 MPa, the number of cycles
to failure is about four and five times larger in CT specimens than in non-treated ones. In addition, the
authors have found that at a maximum stress of 310 MPa (just above the fatigue limit), the number of
cycles to failure has been 2.8105 for non-treated samples whereas subzero treated specimen did not fail
at 1.7107 cycles, (> 60 times longer). In [28], the same material has been pre-strained by 10% and
subjected to the same subzero treatment, obtaining an extension of fatigue life of more than 10 times.
Similar results have been found on AISI 304 (2% and 10% pre-strained) and on AISI 316 samples [29].
The authors have stated that by controlling dislocation density and temperature it is possible to control the
size of martensite in the material; they have also suggested that the nano-sized martensite formed at
intersection of two partial dislocations is effective in pinning dislocation, with the result of extending
fatigue life by prolonging the nucleation phase.











Fracture Toughness

Fracture toughness is a measure of the breaking resistance of a material which contains a crack.
Together with the fatigue behavior, fracture toughness is one of the keys of the design applications of the
last century. As mentioned in the Fatigue Resistance paragraph, retained ductile austenite fraction can
play the role of crack arrestor in martensitic steels, enhancing the toughness. In [13], the authors have
suggested that carbides fraction and dimension and retained austenite fraction play an important role in
the optimization of the ratio between hardness and toughness of high speed steels. The authors did not
performed any test to measure fracture toughness KIC, but they have used a semi-empirical equation
proposed by themselves to calculate it, pointing out a decrease in toughness after CT:



where HRc is the Rockwell-C hardness, fcarb and faust the volume fractions of undissolved eutectic
carbides and retained austenite, E the Young elastic modulus expressed in MPa, and dp is the mean
distance between undissolved eutectic carbides in the matrix. The value of dp has been estimated by
the authors by measuring the mean diameter of undissolved carbides Dp from a 1000 magnification
image obtained with a Scanning Electron Microscope (SEM) and using:.



It is evident that an higher fraction of smaller carbides leads to lower values of dp and KIC. It is also
evident the role played by dp, fcarb and faust in controlling the ratio between HRc and KIC. In contrast
with the results of [13], the Charpy impact tests reported in [17, 18, 44] have shown an increase of KIC on
AISI H13 tool steel after a double tempering and a DCT, without any effect on hardness and impact
energy. The impact toughness before and after DCT on M2 and T1 tool steels has been measured in [16],
obtaining an increase of about 43% and 58% respectively. No DCT effect on toughness has been found
on 4140 cold rolled steel [40]. An evident toughness drop (14.3%) after DCT has been observed in [12]
on AISI 4340 steel; the authors have attributed this decrease to the higher martensite content of the cryo-
treated samples. A slight increase (+11.8%) of the impact toughness J after 48 hours DCT on a 7075
aluminum alloy has been measured in [33], with a confidence level of about 90-95%.


















Evaluation of factors influencing deep cryogenic treatment that affect the
properties of tool steels

1. The most significant factors influencing the properties of tool steels are the austenitizing and
tempering temperatures during conventional heat treatment. Of the parameters relating to deep
cryogenic treatment, only the holding time and the heating rate have a significant effect on the
material properties. The cooling rate is only significant in interactions with the heating rate or the
holding time.

2. The confirmation experiments have shown that only the hardness and the wear behavior are
correct within the 95% confidence interval.

3. When applying DCT to improve mechanical properties such as the bending strength, elongation
at fracture, and deformation work, a low austenitizing temperature in combination with a high
tempering temperature is beneficial. The opposite combination, high austenitizing and low
tempering temperatures, improves both the Vickers hardness and the wear behavior.

4. The wear rate is nearly constant for holding times of up to 24 h. For a longer holding time of 36 h,
the wear rate reaches a minimum and increases again on further holding.










CONCLUSIONS


Cryogenic systems allow to control important cycle parameters such as cooling rate, minimum
reached temperature and soaking time. The choice of optimal treatment parameters requires
specific investigations on each material, but in the case of steels some useful indications can be
inferred from published works;
Wear resistance and hardness improvement have been widely confirmed by published papers,
especially by the ones concerning tool steels. Beneficial effects of CT on toughness and fatigue
behavior have also been claimed by some authors. With few rare exceptions, no noticeable
effects on tensile properties have been found in literature;
Fine dispersed n-carbides precipitation appears to be effective on the wear resistance DCT
improvement of tool steels rather than the retained austenite elimination, that is reached with SCT
too;
The only proposed microstructural mechanism for fine carbides precipitation in tool steels is the
martensite contraction, due to thermal stresses during cooling, which leads carbon atoms to
segregate near lattice defects;
In the fatigue strengthening field, further investigations are necessary, for example, on the nano-
martensite formation mechanism for austenitic steels, on the dislocation pinning effect produced
by a field of fine hard carbides in martensitic steels and on the contribution of retained austenite
and of residual stresses;
CT effect on the thermal and thermo-mechanical fatigue behavior could be an interesting
research field;
Considering the improvements in wear and hardness of PTFE, PI and PEI, further investigations
about the effects of CT on mechanical properties of polymers and composites could be a
stimulating research topic.