Utilization of Cu in

Ferrous Materials

Syarif Junaidi
Dept. Mechanical & Materials Eng.
National University of Malaysia
 Presentation content
1. Introduction
2. Objectives
3. Strengthening Mechanism
4. Effect of Cu in solid-solution
5. Advantage of Cu nanoparticles
6. Combination of nano steel (ultra fine
grained steel) and Cu nanoparticles
7. Summary
• In Japan, the amount of steel scraps reached 1billion ton (2000),
on the other hand, Japan’s steel production : 100million ton/year.
(Japan has “natural resource” of steel for 10 years)

• The recycling of steel scraps is retarded because the scraps are contaminated
by Cu which is difficult to be eliminated.

• Accumulation of the scraps becomes national problem in Japan.

 Does Cu have advantage? (Fe-Cu binary alloy)

wide γ single phase

910ο
C γ

wide α 850ο
single phase α
C
γ +ε
Cu
•No intermetallic phase
•Pearlitic structure or fine second phase
•Exhibit martensitic transformation
•Effect of heat treatment and cooling
rate?

0 1.8 4 Cu (mass%)
Fe-Cu phase diagram is similar to Fe-C phase diagram
Objectives:
In terms of the promotion of recycling steel
scraps, Cu has been tried to be utilized as an
effective alloying element.

Some of utilization of Cu such as solid solution

strengthening and precipitation strengthening will
be introduced in the presentation.
trengthening Mechanism
How to increase the strength of metals?
Illustration of Strengthening Mechanism in steel
Dislocations (cars on highway) move
easily within a steel

To disturb motion of car = To increase strength = strengthening

Solid solution strengthening Solute Cu

bumpy road

Precipitation strengthening Cu nanoparticles

riverbed road

Dislocation strengthening Cold-rolled steel

traffic jam

Grain refinement Ultrafine grained

strengthening steel with
Cu nanoparticles
dead-end road
fect of Cu in solid-solution

Why do we utilize Cu in solid-

solution?
Heat treatment of Cu bearing steel
Solution treatment Aging
γ
α +ε C
W.Q u

α +ε C
u
α or α ’ (single phase)
+ solute Cu
(super saturated)
Effect of solute Cu on microstructure (ferritic steel)
Steel: Fe-0~2%Cu alloy
Pure iron 1%Cu steel

2%Cu steel

Ferrite single phase (Cu in solid solution)

Ferritic grains are refined owing to Cu addition
Effect solute Cu on microstructure and mechanical properties

8%Ni 8%Ni-1%Cu 8%Ni-3%Cu

Microstructure of martensite

200µ m

Structures are refined as Cu content increases

Prior γ grain sizes tend to decrease

Effect solute Cu on yield strength
Cu content, [Cu] / mass%
0 0.5 1.0 2.0 3.0
750

Martensitic steels
700
0.2% proof stress, σ / MPa

17×[at.%Cu]1/2 The addition rule is not suited

650
to the case of the martensitic
0.2

Cu steel
600

200
Ferritic steels

150
The influence of the solid
solution strengthening by Cu
57×[at.%Cu]1/2 clearly decreases
100
Solid solution strengthening
50
0 0.5 1.0 1.5 2.0
(Cu content; [Cu])1/2 / (at.%)1/2 J. Syarif, K. Nakashima, T. Tsuchiyama
and S. Takaki, ISIJ International, 2007, 2
Difference of strengthening mechanism between the
ferritic steel and the martensitic steel
Ferritic steel Martensitic steel

θb
θb

Solute Cu dislocation Solute Cu dislocation

dislocation

Solid solution strengthening Dislocation strengthening

vantage of Cu nanoparticles
How strong is it? Useful?
 873K-162ks

Precipitation strengthening of Cu

K.NAKASHIMA et. al, ISIJ International, Vol. 42 (2002), No. 12,

E. Hornbogen and R.C. Glenn : Trans. Met. Soc.
AIME, 218(1969), 1064 pp. 1541–1545
Precipitation behavior of Cu
During aging, Cu in solid solution will transform to
bcc Cu  9R  3R  fcc(ε ) Cu

P.J. Othen, M.L. Jenkins, and G.D.W. Smith: Phil. Mag., 1994, vol. 70, pp. 1–24.
Precipitation strengthening of Cu nanoparticles

What is strengthening mechanism of Cu nanoparticles??

Mechanism of precipitation strengthening
When a moving dislocation is pinned by
dispersed precipitates as shown in
Figure, shear stress (∆ τ ) required for
bowing the dislocation with angle θ is
expressed by the Eq. (1).

∆τ = (α Gb/λ )sinθ .................. (1)

Tensile stress (∆ σ ) is given by multiplying Taylor factor to the shear stress and
expressed using another constant (b) as follows:

∆ σ =(β Gb/λ )sin θ ............................

(2)
Carbon steels with carbide: β =2.8, because θ = π /2.
Mean particle spacing; λ was calculated with the Eq. (3).

λ =1.25(π dp3/6fdp)1/2 - (π dp2/4dp)...........................(3)

Where dp is diameter of the precipitates. The f is volume fraction of the precipitates
Mechanism of precipitation strengthening

Bowing degree of Cu nanoparticles is smaller

than π /2

Not the Orowan mechanism, so?

Mechanism of precipitation strengthening
1. Strong obstacles

θ =
π /2

2. Weak obstacles (Cu nanoparticles)

θ <
π /2

Conversely, dislocation cuts Moreover, Kelly proposed

off the particles for passing
trough. Thus, θ <π /2.
Strengthening due to
differing Elastic
modulus between
matrix and particle
tilization of Cu nanoparticle
in structural steels
Are the properties changed??
1. HSLA steels
Chemical compositions of the steel

TMCP
1150ο C

Tf : 910, 910ο C-1hr γ

850, 723ο C
350-690ο C-1hr γ +α

Accelerated α +ε
cooling Cu
W.Q.

DQ RQ
Microstructure of Cu bearing HSLA steels

RQ DQ, 910ο C

DQ, 850ο C DQ, 753ο C

HSLA steels aged at 630ο C

ε −Cu nanoparticles
HSLA steels
Recent development,
Sumitomo corp has patented YP480 MPa plate steel for offshore use
(fulfilled API standard) by Cu addition.

One of the largest steel companies in Japan has been developing

YP550MPa.

Why?
1. Cu can substitute C, thus weldability will be improved
2. C u increases the strength without deteriorating ductility
2. Utilization of Cu in a cryogenic steel
Steel: Fe-9%Ni-0.1%C-0~3Cu alloy
1223K-3.6ks
873K-3.6ks γ

α +γ +ε C
W.Q u

α +γ +ε C
u

Cu nanoparticles
Utilization of Cu in a cryogenic steel

The improvement of strength–ductility balance in Cu bearing 9%Ni steels are

derived from
1. Strengthening of martensitic matrix by precipitation strengthening by Cu
particles
2. an increase in uniform elongation due to the rise of work-hardening rate
caused by TRIP assisted effect of reversed .
3. Utilization of Cu in Heat-Resistant Steel
Steel: Fe-9%Cr-(0~4)%Cu alloy 1223K~14
23K-3.6ks γ

W.Q

Full martensitic
structure
Utilization of Cu in Heat-Resistant Steel 1223K-3.6ks
873K-140MPa γ

α +ε Cu
W.Q

Creep-properties is improved owing

to Cu nanoparticles
mbination of Cu nanoparticl
and ultrafine grain
The ultimate
method??
Ultra-fine grained steel
M.M
Steel: Fe- 1.5%Cu-3vol%Y2O3

mixing

Cu powder
Tubing

Iron powder Yttria powder

773K

α +ε
Cu

Hot rolling
Aging
Addition Cu in Ultra-fine grained steel

Cu nanoparticles within UFF grain Effect of Cu is not significant

Why? It is thought that

1. Hardness of UFG steel is too high,
2. Addition rule of the strengthening mechanism cannot be applied
Summary
It is shown that addition of Cu can improve the mechanical
properties of ferrous materials for structural use.

Both of solid solution and precipitation states, Cu can increase

the hardness of the steels. Moreover, the strength-ductility
balance is also improved in the low alloy and cryogenic steel.

On the other hand, the effect of Cu nanoparticles is inferior in

the ultra-fine grained steel.

Recommendation
Few works have been done to clarify the effect of Cu
nanoparticles on wear behavior and fatigue properties of steels.
Effect solute Cu on low temperature toughness

solute Cu
Fractography of sample
Charpy-tested at -50oC

1%Cu steel Pure iron

Pure iron: cleavage fracture (brittle)

1%Cu steel: dimple (ductile)
Microstructure of near fracture surface
Pure iron 1%Cu steel

Pure iron 1%Cu steel

In -50ο C:
Pure iron: twin deformation
1%Cu steel: slip deformation due to dislocation
DBT behavior of 8Ni-Cu steels