1. Introduction
Titanium and its alloys are vital for future developments due to their high strength-to-weight ratio, remarkable corrosion resistance, high toughness, good resistance to fatigue, excellent biological compatibility, and the ability to withstand moderately high temperatures without creep [
1,
2,
3,
4]. Titanium alloys have found a wide range of applications in many industries aerospace, power generation, chemical processing, heat exchangers, medical applications, sports, and automotive. However, the high production cost of titanium is a significant obstacle restricting its widespread use in everyday applications. Titanium parts manufactured by ingot metallurgy cost approximately four times more than their steel counterparts [
2]. Therefore, there is a great impetus to explore alternative manufacturing routes that can offer higher levels of material utilisation through near-net shape processing coupled with minimum machining.
Powder metallurgy (PM) is one such technique that avoids costly melt processes and shorter procurement lead times. It increases the utilisation of the material to 95%, resulting in an estimated 20–50% cost savings compared to conventional parts [
5]. Besides the economic efficiency, PM can produce complex shape parts with a high degree of freedom in the selection of alloy composition and resulting in desired uniform microstructure characteristics. Many established PM methods exist for consolidating metal powders [
6,
7,
8,
9,
10,
11,
12,
13]. Thermomechanical powder consolidation (TPC) processes (such as powder extrusion and forging) are a natural extension of the conventional press and sinter process. Here, the desired final shape of the part is obtained from extrusion or forging procedure using sintered compacts. During TPC processes, particles in the powder compact plastically deform to offer several advantages, including the elimination of pores present after sintering, refinement of grain size, and deformation of the prior particle surfaces. The deformation causes a change in particle shape to fill the gaps better and assist the joining of particles by creating new particle surfaces. Therefore, the resulting final part is fully dense and has unique microstructure and mechanical properties [
14,
15,
16].
Ti-6Al-4V is the most commonly used alloy, accounting for more than 50% of total titanium usage worldwide and therefore referred to as the workhorse of the industry [
2]. Ti-6Al-4V alloy is an excellent candidate for aerospace applications due to its mechanical properties, which can be altered by changing processing conditions or with appropriate heat treatment [
2,
17]. The mechanical properties can be controlled by refining the amount and distribution of α and β phases [
17]. Typical tensile properties of the grade five Ti-6Al-4V alloy can range between 800–1100 MPa yield strengths and 896–1200 MPa ultimate tensile strength, while the material’s ductility varies between 10–16% [
2,
17]. Unlike the extensive discussion and analysis on the static properties of Ti-6Al-4V alloy [
2,
13,
18,
19], there is little discussion in the literature on the dynamic properties, including the impact properties of PM-produced Ti-6Al-4V alloy. Many applications for these powders produced titanium materials where fracture-related properties such as impact properties and fracture toughness are essential. Due to this reason, a broad spectrum of available literature values of the impact energy is included in this section to assess the Ti-6Al-4V alloy performance at high strain rates [
20,
21,
22,
23,
24,
25]. From
Figure 1, it is clear that Extra Low Interstitial (ELI) ingot Ti-6Al-4V alloy can have impact energy values in the range of 24~40 J, and standard grade five Ti-6Al-4V alloy can achieve toughness 20~27 J.
According to the studies by Zherebtsov et al. and Reda et al., the impact toughness of as-processed Ti-6Al-4V alloy by casting and multi-axial forging can be 11 J and 18 J, respectively [
23,
24]. Regarding PM-produced Ti-6Al-4V alloy, hot isostatically pressed PREP powder can provide superior impact energy of around 48 J compared to ingot or other PM routes such as SLM [
21,
22]. The significant research performed by the author on Ti-6Al-4V alloy fabricated using the TPC route reveals that impact toughness in the range of 9.7–21 J can be achieved depending on the level of oxygen impurity contents and type of heat treatments employed [
28,
29,
30,
31,
32]. Generally, low impurity content and optimized microstructures result in high-impact toughness. Meyer et al. showed that furnace cooling of the material from 955 °C is an effective way to enhance the impact properties of a mill-annealed wrought Ti-6Al-4V alloy [
33].
In the literature, it is reported that sub-transus annealing treatments of TPC-produced Ti-6Al-4V alloy can achieve lamellar type microstructures with desirable grain, colony, lamellar α, and grain boundary α morphology to enhance the fracture-related properties despite the presence of high oxygen impurity (0.33–0.42 wt.%) in the material [
30,
31]. Oxygen is an α stabilizer that increases the β transus temperature and promotes the formation of α precipitates during subsequent cooling [
2]. No study in the literature provides impact data for powder-produced Ti-6Al-4V alloy with oxygen impurity contents above 0.43 wt.%. Therefore, the effectiveness of these sub-transus annealing on PM-produced Ti-6Al-4V alloy with extremely high impurity contents is still unknown. The focus of the current study is to determine the level of mechanical properties obtainable through sub-transus annealing treatments (955 °C/1 h-furnace cooling and 925 °C/4 h-cooling @ 50 °C/h to 760 °C-furnace cooling) for Ti-6Al-4V alloy which contains 0.55 wt.% oxygen impurity and produced using TPC route.
2. Materials and Methods
The nominal composition Ti-6Al-4V was obtained by blending the 9:1 weight ratio of elemental hydride-dehydride (HDH) titanium powder and master alloy powder (MA-60 wt.%.Al-40 wt.%V). The measured oxygen impurity contents and particle size of these starting powders are displayed in
Table 1. A three-stage roller mixing approach was deployed to blend 5 kg raw powders homogeneously without a suitable capacity powder mixing equipment. During the first stage, ten separate batches containing 500 g of powder mixture with stainless steel balls (2:1 weight ratio to powder) were added to an airtight plastic container to assist in the blending process. A roller mill was used to rotate this container at a speed of 200 rpm for 24 h. After completing the mixing cycles, the compositional homogeneity of these individual mixes was further enhanced by adding five of these 500 g mixes into a large capacity airtight plastic container. Two batches containing 2500 g of powder mixed with an appropriate volume of stainless-steel balls were again milled for 24 h using the same speed and roller mill. For the final mixing stage, the powder mixture from both batches was transferred to a new larger container after sieving the stainless-steel balls. This container was manually stirred for sufficient time to achieve a single Ti-6Al-4V powder batch of five-kilogram quantity.
The blended powder mixture was consolidated using the sequence of thermomechanical processing operations schematically illustrated in
Figure 2. The uni-axial warm compaction of the blended powder mixture was performed at 260 °C in air, with a compaction pressure of 450 MPa. The inner surface of the compaction die and plunger were coated with colloidal graphite lubricant to reduce die-wall friction. The resulting green cylindrical powder billet had a diameter of 102 mm and a height of 148 mm. Based on these dimensions and its mass, the relative green density of the billet was calculated to be between 84–86%. To perform the final extrusion of the green billet in the air, it had to have further consolidation using vacuum sintering (to get a relative density of ~93%). The sintering was performed using a commercial scale vacuum furnace ZSJ—35 × 35 × 70 (manufactured by Advanced Corporation for Materials & Equipments Co. Ltd. (ACME), MuYun Industrial Zone, Changsha, China). The four-step sintering cycle was adopted. In the first step, the green billet was heated to 260 °C at a heating rate of 10 °C/min. Step two was an isothermal hold of 6 hrs to achieve a high vacuum, in the range of 1–3 × 10
−2 Pa. Step three involves heating billet at a heating rate of 10 °C/min to 1400 °C. In the final step, the isothermal hold time was selected to be 3 h, followed by natural furnace cooling (FC) to room temperature. For hot extrusion, the vacuum-sintered billet was heated to a temperature of 1150 °C using an induction coil in air. A protective layer of high-temperature glass was applied to the surface of the vacuum-sintered billet to prevent oxidation before extrusion. The hot billet was manually shifted to a well-lubricated cylindrical extrusion chamber, which along with the die, was already at 420 °C. The ram of a 700-ton vertical hydraulic press was used to push the billet through a rectangular profile extrusion die, with a cross-sectional area that resulted in an extrusion ratio of 9:1. As-extruded bar had a cross-sectional dimension of 36 mm (W) × 16 mm (H) and a length (L) of 1000 mm.
The material characteristics, including actual chemical composition and oxygen impurity contents of as-extruded material, were obtained by X-ray fluorescence (Spectro Xepos spectrometer, SPECTRO Analytical Instruments, Kleve, Germany) and LECO inert gas fusion method, respectively. The processed rectangular bar was cut into multiple appropriate lengths, and the oxygen-enriched outer α-case layer from each section was machined off before the post-extrusion annealing treatments. In the first sub-transus annealing treatment 955 °C/1 h-FC (now onward referred to as HT-A), the material was heated to 955 °C followed by a one-hour isothermal hold. It was then furnace cooled to room temperature. The second sub-transus heat treatment (925 °C/4 h-cooling @ 50 °C/h to 760 °C-FC) consisted of annealing at 925 °C for 4 h, followed by a controlled furnace cooling at a cooling rate of 50 °C/h to 760 °C, then natural furnace cooling to room temperature. This condition will be referred to as HT-B.
The selected sub-transus annealing temperature (925–955 °C) and isothermal holding time are designed to adjust the α volume fraction. In contrast, the cooling rate and secondary cooling stage to 760 °C is selected to change the width and length of α lamellae substantially. Both heat treatments were performed in a vacuum furnace (ACME, ZSJ—20 × 20 × 30) (Advanced Corporation for Materials & Equipments Co. Ltd. (ACME), MuYun Industrial Zone, Changsha, China). The microstructures of as-extruded along with heat-treated material were observed using an optical microscope (Olympus BX60, Olympus Optical Co Ltd, Tokyo, Japan) and a scanning electron microscope (SEM) (Hitachi S-4700, Tokyo, Japan). The ground and polished samples for optical and SEM were etched in a modified Kroll’s reagent consisting of 2 vol.% HF, 4 vol.% HNO3, and 94 vol.% H2O.
Multiple flat dog-bone-shaped tensile test specimens with a square cross-section of 1.8 × 1.8 mm and a gauge length of 20 mm were prepared from longitudinally orientated material. Tensile testing was carried out at room temperature using an Instron 4204 universal machine (Instron, Norwood, MA, USA). The strain was measured using a clip-on extensometer with a gauge length of 10 mm, and tests were done using a strain rate of 1 × 10−4 s−1.
The high strain rate performance data for the material under a tri-axial stress state was obtained using standard Charpy impact specimens with dimensions 10 mm × 10 mm × 55 mm were machined, and a 2 mm deep v-notch (with an approximate tip radius of 0.25 mm) was introduced as specified in the ASTM standard E23-07. Impact testing was performed at room temperature using an Avery-6703 impact tester (Avery Denison, United Kingdom) with a maximum energy rating of 300 J, an impact velocity of 5 m/s, and a margin of error of ±2 J. The fracture surfaces of impacted specimens were examined using a Zeiss Evo MA25 SEM (Jena, Germany). Additionally, an impact specimen tested in the as-extruded and each heat-treated state were sectioned longitudinally (perpendicular to the crack propagation direction) to study the crack propagation mechanism. The samples attained in this manner were cold-mounted using a vacuum impregnation system using self-curing epoxy resin before mechanical grinding, polishing, and etching with Kroll’s reagent. An Olympus BX60 (Olympus Optical Co Ltd, Tokyo, Japan) optical microscope was used to examine the microstructural features present along the crack path.
Author Contributions
Conceptualization, A.P.S. and B.G.; methodology, A.P.S.; formal analysis, A.P.S. and G.S.; investigation, A.P.S.; resources, B.G.; data curation, A.P.S.; writing—original draft preparation, A.P.S.; writing—review and editing, R.T., G.S. and B.G.; visualization, A.P.S.; supervision, B.G. and R.T.; project administration, B.G.; funding acquisition, B.G. All authors have read and agreed to the published version of the manuscript.
Funding
This research was funded by the Ministry of Business, Innovation, and Employment (MBIE), New Zealand, grant number UOWX1402.
Data Availability Statement
Not applicable.
Acknowledgments
The authors would like to take opportunity to express their great indebtedness to the Titanium Industry Development Association (TiDA) for providing immense technical support for experimental work. The authors’ sincere thanks also go to Aamir Mukhtar for the timely support and guidance.
Conflicts of Interest
The authors declare no conflict of interest. Also, the funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.
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Figure 1.
Impact toughness (range) of Ti-6Al-4V alloy produced by various ingot and PM methods [
20,
21,
22,
23,
24,
25,
26,
27,
28,
29,
30,
31,
32].
Figure 2.
The sequence of operations used to prepare the Ti-6Al-4V alloy bar using a combination of warm compaction, vacuum sintering, and a blended powder mixture extrusion.
Figure 3.
Optical micrograph showing a typical lamellar/Widmanstätten type structure of Ti-6Al-4V alloy attained after air cooling from β phase field.
Figure 4.
Fully lamellar microstructure attained after HT-A (furnace cooling from 955 °C) (a) overall appearance (b) morphology of individual α platelets and retained β phase matrix.
Figure 5.
Micrographs showing equiaxed β grains with colonies of α and lamellarα developed after HT-B (925 °C/4 h-@50 °C/h to 760 °C-FC) (a) Low magnification micrograph from the optical microscope (b) dark field image showing the distribution of β phase.
Figure 6.
Typical stress and strain curves of as-extruded and heat-treated Ti-6Al-4V alloy produced using thermomechanical powder consolidation (TPC) route.
Figure 7.
Histogram showing the variation in the Charpy impact toughness values of Ti-6Al-4V alloy in the as-extruded condition and after two different heat treatments.
Figure 8.
Fractographs of Charpy impacted specimens of Ti-6Al-4V alloy (a,b) as-extruded (c,d) HT-A heat treated (e,f) HT-B heat treated.
Figure 9.
SEM fractographs showing the presence of ductile dimples in HT-A impact toughness specimen.
Figure 10.
Crack propagation behaviour of impacted specimens (a,b) as-extruded (c,d) HT-A (e,f) HT-B, here images (a,c,e) shows a general appearance and (b,d,f) illustrates the behaviour of the crack within individual grains.
Table 1.
Particle size and oxygen impurity content of starting powders.
Start Materials | HDH Titanium | Master Alloy (Al60-V40) |
---|
Particle size | −200 mesh | −250 mesh |
Mean particle size (d50) | 51.25 µm | 35.88 µm |
Oxygen impurity content (wt.%) | 0.23~0.25 | 0.61~0.67 |
Table 2.
Measured chemical composition and oxygen content of the extruded Ti-6Al-4V bar.
Material | Composition [wt.%] |
---|
Ti | Al | V | O |
---|
As-extruded Ti-6Al-4V | 90.65 | 5.60 | 4.25 | 0.55 |
Table 3.
Summary of average tensile properties obtained for as-extruded and annealed Ti-6Al-4V alloy prepared from blended powders using thermomechanical powder consolidation (TPC) route.
Sample | Yield Strength (MPa) | Ultimate Tensile Strength (MPa) | Elongation to Fracture (%) |
---|
As-extruded (AE) | 956 ± 30 | 1150 ± 97 | 2.4 ± 0.7 |
HT-A | 993 ± 12 | 1181 ± 44 | 3.2 ± 0.5 |
HT-B | 992 ± 11 | 1164 ± 22 | 2.3 ± 0.5 |
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