Scripta Materialia 45 (2001) 747±752

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Advanced mechanical properties of pure titanium with

ultra®ne grained structure
A.V. Sergueevaab, V.V. Stolyarovb, R.Z. Valievb, and A.K. Mukherjeea*
a
Department of Chemical Engineering and Material Science, University of California, Davis, CA 95616, USA
b
Institute of Physics of Advanced Materials, Ufa State Aviation Technical University, 12 Marks str., Ufa 450000, Russia
Received 5 February 2001; accepted 17 May 2001

Abstract

The mechanical properties of commercially pure (CP) Ti at room temperature were investigated. The
decreasing grain size in CP Ti leads to signi®cant increases in its hardness and/or strength. A combination
of severe plastic deformation by high pressure torsion at 5 GPa followed by short annealing at low tem-
peratures allows one to obtain a high strength (more than 1200 MPa) in pure material that is comparable
in strength to alloyed Ti. Ó 2001 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights
reserved.

Keywords: Ultra®ne-grained materials; Titanium alloy; Mechanical properties

Introduction

Grain size is well known to have a profound e€ect on the mechanical behavior of
materials, in particular, on the strength characteristics. The re®nement of the micro-
structure allows one to increase strength of materials without change in chemistry, i.e.,
without alloying. In some cases this can be a very important consideration. For ex-
ample, pure Ti component is a more acceptable material for biomedical applications
than its alloys [1] if its strength can be raised by a factor of two or more. Recent in-
vestigations [1±4] were aimed at providing such increase in strength in pure Ti. The
promising technique for signi®cant re®nement of the microstructure in bulk materials
is severe plastic deformation (SPD) [5]. The methods of SPD, such as equal channel
angular pressing (ECAP) and high pressure torsion (HPT), allow one to form a mi-
crostructure with grain sizes less than 500 nm and with high density of the processed
material.

*
Corresponding author. Fax: +1-530-752-9554.
E-mail address: akmukherjee@ucdavis.edu (A.K. Mukherjee).

1359-6462/01/$ - see front matter Ó 2001 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 6 4 6 2 ( 0 1 ) 0 1 0 8 9 - 2
748 A.V. Sergueeva et al./Scripta Materialia 45 (2001) 747±752

The present paper demonstrates the dependence of mechanical properties of CP Ti

on grain size at ambient temperature and the possibility of signi®cantly increasing its
strength using thermo-mechanical treatments based on SPD.

Experimental

A commercially pure (CP) titanium (0.12%O; 0.18%Fe; 0.07%C; 0.04%N; 0.01%H;

balance Ti) was subjected to SPD by HPT and disks of 10 mm in diameter were ob-
tained. Details of SPD processing were reported earlier [5,6]. Deformation by HPT of
CP Ti was performed at ambient temperatures under a pressure of 5 GPa. The mi-
crostructures of as-processed and annealed specimens were investigated by transmission
electron microscopy (TEM). Thin foils were prepared by jet-polishing with an elec-
trolyte consisting of 6% perchloric acid, 35% butyl alcohol and 59% methanol by
volume. The microhardness …Hv † was evaluated using a Vickers diamond pyramidal
indenter with a load of 0.2 kg. The tensile tests were performed on a custom-built
computer controlled constant strain rate tensile test machine with a displacement reso-
lution of 5 lm and a load resolution of 0.1 N. Tensile specimens with a 1-mm gage
length  1 mm width were electro-discharge-machined from disks.

Results and discussion

Bright and dark ®eld TEM micrographs and selected area electron di€raction
(SAED) pattern, obtained from region with a diameter of 1 lm, of as-processed CP Ti
are shown in Fig. 1. The microstructure is suciently homogenous but there is evidence
of signi®cant lattice distortions associated with high internal stresses. The light areas on
dark ®eld images have non-uniform contrast. Most of the grain boundaries are poorly
de®ned. That makes it a dicult task to estimate the true grain sizes. The di€raction
pattern presents numerous spots arranged in circles that is typical for a ®ne granular
type microstructure with high angle grain boundaries and signi®cant spreading of spots
con®rms the existence of high internal stresses [5]. The sizes of fragments separated by

Fig. 1. Typical bright ®eld (with SAED as an insert) (a) and dark ®eld (b) micrographs of as-processed SPD CP Ti.
 A.V. Sergueeva et al./Scripta Materialia 45 (2001) 747±752 749

large misorientation have been estimated by dark ®eld images and it is about 120 nm.
But as was mentioned earlier [7], the small light areas observed in the dark ®eld images
do not depict their true size because of distorted layers at the periphery of each grain.
The actual grain size is slightly larger.
Most of UFG (submicro- and nanocrystalline) materials processed by SPD have
demonstrated enhanced hardness and strength at room temperature [5]. For conven-
tional polycrystals with grain sizes ranging from several to hundreds of micrometers,
the hardness and the strength dependences on mean grain size can be described by
Hall±Petch relations:
H ˆ H0 ‡ k 0 d 1=2

or
1=2
ry ˆ r0 ‡ kd ;
where H is the hardness; ry is the yield stress; d is the average grain size; H0 , r0 and k
and k 0 are material constants. The mechanical behavior of materials with smaller grains
is still being discussed in terms of various models. Some studies have revealed mate-
rials softening with decreasing grain size (negative slope of Hall±Petch-like relation-
ships) [8,9], while the usual relation (positive slopes) have been found in others [10±12].
Fougere et al. [13] noticed that the hardening and softening of UFG materials can
depend upon the method to vary the grain size. For example, in samples prepared by
the inert gas condensation and consolidation method voids may be annealed out,
thus leading to a hardness increase. This was illustrated in Cu prepared by the inert
gas condensation and consolidation method and then annealed [13]. Annealing clearly
hardens the nanocrystalline Cu as the grains grow and therefore an apparent ``inverse''
Hall±Petch curve can be observed.
A similar result was reported by Mishra et al. [16] and by Valiev et al. [17] in ®ne-
grained Al±1.5%Mg alloys prepared by severe plastic deformation. Annealing the 150
nm grain size as-deformed samples initially increased the hardness without changing
the grain size. When grain growth began the hardness also dropped. The authors [17]
suggested that the hardening observed on annealing is due to the initial state of grain
boundaries, which may be transparent to mobile dislocations. Such grain boundaries
became more nearly in an equilibrium state upon annealing. Fig. 2 summarized the
published data on variation of room temperature microhardness with a grain size for
CP Ti. Our data for as-prepared state of CP Ti after HPT are included. It is seen that, in
general, the experimental results follow a Hall±Petch relationship up to grain size of
10 nm. The hardness of CP Ti increases with re®nement of microstructure.
The in¯uence of average grain size of CP Ti on its mechanical behavior during tensile
tests is shown on Fig. 3. All tensile tests were performed on small samples with the gage
thickness of 0.1 mm. The grain size of 50 lm in CP Ti was obtained after annealing of
rolled foil in vacuum [18]. The samples with grain sizes of 5 lm and 100 nm were tested
in as-deformed state. The decreasing grain size leads to signi®cant increase in strength
combined with good ductility. The increased strength of HPT-processed Ti in this case
is related not only to average grain size but also to e€ect of severe deformation. Table 1
750 A.V. Sergueeva et al./Scripta Materialia 45 (2001) 747±752

Fig. 2. Room temperature microhardness vs. grain size for CP Ti from Refs. [3,4,14,15] and current investigation.

3
Fig. 3. Stress±strain curve for CP Ti with di€erent grain size at room temperature and strain rate 10 s 1.

is a summary of room temperature tensile properties of CP titanium with UFG

structure obtained by di€erent methods of SPD. In all cases the properties relate to as-
deformed state.
Table 1 shows the potential for strength and ductility of pure material. It is seen that
SPD leads to signi®cant re®nement of microstructure and increase in strength with
good ductility.
An interesting result was obtained on HPT processed titanium after short annealing
at low temperatures (250°C and 300°C). Fig. 4 exhibits the e€ect of such treatment on
mechanical characteristics of CP Ti at room temperature in comparison with the as-
prepared state (a grain size is about 100 nm) shown on Fig. 3. After low temperature
annealing the ultimate strength of pure Ti exceeds 1200 MPa that is close to strength of
many Ti alloys. Moreover, the ductility is still adequate. After annealing at 300°C for 10
 A.V. Sergueeva et al./Scripta Materialia 45 (2001) 747±752 751
Table 1
Mechanical properties of CP Ti at room temperature
State Method of SPD Average grain UTS YS Elongation References
size (nm) (MPa) (MPa) (%)
1 ECAPa 280 710 640 14 [3]
2 ECAP ‡ cold rolling (75%)a 100b 1150 1020 8 [4]
3 ECAP ‡ HPT (1.5 GPa) 200 730 625 25 [5]
4 HPT (5 GPa) 120 950 790 14 Current result
a
Tensile tests were carried out on standard samples with 5 mm in diameter.
b
The mean width of elongated grains.

Fig. 4. Stress±strain curves for CP Ti in as-prepared and annealed state at room temperature.

Fig. 5. Bright ®eld (with SAED as an insert) (a) and dark ®eld (b) micrographs of SPD-processed CP Ti after annealing
at 250°C for 10 min.

min the ultimate strength of CP Ti is 1240 MPa and the ductility is more than 20%.
Further increase of annealing temperature leads to decrease in strength. Similar e€ect of
annealing on mechanical properties of some materials subjected to SPD has been re-
ported earlier [7]. An analysis of the in¯uence of a short annealing on microstructure of
HPT processed Ti revealed important changes compared to as-prepared state (Fig. 5).
752 A.V. Sergueeva et al./Scripta Materialia 45 (2001) 747±752

There is evidence of signi®cant decrease in lattice distortions without visible grain

growth (mean grain size is about 150 nm after annealing up to 300°C). This is con®rmed
by SADP where the level of asterism or streaking of di€raction spots is decreased. The
grain boundaries became well de®ned with more uniform contrast.

Conclusion

The decreasing grain size in CP Ti leads to signi®cant increases in its hardness and/or
strength. A combination of SPD by HPT at 5 GPa followed by short annealing at low
temperatures allows one to obtain a high strength (more than 1200 MPa) in pure
material that is comparable in strength to alloyed Ti. Furthermore, the material pro-
cessed in such a manner retains adequate ductility (more than 20%). Hence, the de-
velopment of SPD methods with subsequent heat treatment appears to be a promising
approach for producing advanced materials for strength-intensive service applications,
e.g., in biomedical areas.

Acknowledgements

This investigation was supported by a grant from the US National Science Foun-
dation (NSF-DMR-9903321).

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