Authors Accepted Manuscript

Sustainable production of Titanium foams for

biomedical applications by Concentrated Solar
Energy sintering

I. Garca, E. Gracia-Escosa, M. Bayod, A. Conde,

A. Arenas, J. Damborenea, A. Romero, G.
Rodrguez
www.elsevier.com

PII: S0167-577X(16)31494-X
DOI: http://dx.doi.org/10.1016/j.matlet.2016.09.037
Reference: MLBLUE21475
To appear in: Materials Letters
Received date: 16 June 2016
Revised date: 17 August 2016
Accepted date: 10 September 2016
Cite this article as: I. Garca, E. Gracia-Escosa, M. Bayod, A. Conde, A. Arenas,
J. Damborenea, A. Romero and G. Rodrguez, Sustainable production of
Titanium foams for biomedical applications by Concentrated Solar Energy
sintering, Materials Letters, http://dx.doi.org/10.1016/j.matlet.2016.09.037
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 Sustainable production of Titanium foams for biomedical

applications by Concentrated Solar Energy sintering

I. Garcaa*, E. Gracia-Escosaa, M. Bayoda, A. Condea, A. Arenasa, J. Damboreneaa, A. Romerob, G.

Rodrguezb

a
Surface Engineering, Corrosion and Durability Department, National Center for Metallurgical

Research (CENIM-CSIC), Avda. Gregorio del Amo 8, E28040 Madrid, Spain

b
E.T.S Ingenieros Industriales, Universidad de Castilla-La Mancha (ETSII-UCLM), Avda. Camilo

Jos Cela s/n, E13071 Ciudad Real, Spain

*
Corresponding author. igarcia@cenim.csic.es

Abstract

Porous Titanium foams were successfully sintered using a solar parabolic concentrator, of

vertical axis and 2 kW power, in argon atmosphere. Green pellets were previously prepared

following the space holder powder manufacturing route using NaCl as soluble spacer. Titanium

foams were fully sintered at lower temperature and shorter time than in conventional furnace

sintering. Moreover, porosity achieved ranges between 58 and 77 %, with dual size range:

larger porous ranging from 500 to 1000 m resulting from the NaCl particles; and smaller

porous of 1 to 10 m due to the powder sintering. Both the porosity and the porous size

obtained for titanium foams produced by solar sintering fulfil the requirements for load-

bearing and scaffold applications in tissue engineering.

Graphical abstract
Keywords: Biomaterials, Powder technology, Porous materials, Sintering, Solar Energy,

Titanium

Introduction

Titanium and Titanium alloys are excellent biomaterials in spite of their high stiffness

compared to cortical bone, which induces failures of prosthetic implants due to the stress-

shielding between the bone and the implant [1]. However their mechanical properties can be

modulated and tailored by using cellular solids or foams by controlling the open and closed

porosity; the pore size distribution; and the pore morphology [2, 3]. For biomaterials
applications, 50% porosity matches mechanical properties similar to cortical bone, while 80%

matches behaviour of the trabecular bone. Moreover, porosity is also favourable for the

osseointegration of the implant, which is the critical factor for long-term reliability of the

implant [4].

Regarding the manufacturing routes to produce reliable titanium foams, several authors have

recently used a relative simple powder metallurgy technique. By using space holder materials

such as NaCl or other soluble materials, titanium foams have been successfully produced. [5-

7].

On the other hand, Concentrated Solar Energy (CSE) is a clean, renewable, non-polluting and

high efficient technology for high-temperature materials processing. In particular, CSE has

shown great efficiency in steels heat treatment to produce microstructural modifications [8],

nitriding process of titanium alloys [9, 10], NiAl Self Propagating High Temperature Synthesis

(SHS) coatings on carbon steels [11], and steel [12] or Ti6Al4V welding [13]. Moreover, CSE

sintering of steel and reinforced steel have been performed with a notable reduction in

processing time [14, 15].

This work is the first feasibility study of the application of CSE for the sintering of Ti foams

using the powder metallurgy route of space holders, to be used as scaffolds for biomaterial

applications.

Experimental

Ti-powder (purity 99.9%, size < 53 m) was mixed with NaCl crystals of cubic shapes (sieved

between 600 and 1000 m) and a 2%wt of PVA aqueous solution as organic binder. Both were

uniformly mixed in different weight proportions to obtain a nominal volumetric content of 60,

70 and 80 % of NaCl in the titanium matrix. The powder mixture was cold compacted at a
pressure of 300 MPa for 2 min. The compacted green pellets were of 20 mm in diameter and

15 mm height. Then, the green pellets were dried at 100C for 2 h, heated to 400 C for 2 h to

remove the PVA, subsequently immersed in hot water at 80C for 18 h to dissolve the space

holder and finally dried at 100 C for 2 h.

The sintering processes were performed with a solar furnace of 2 kW equipped with a vertical

axis parabolic reflector of 1.5 m diameter at PROMESCNRS Four Solaire (Font Romeu-Odeillo,

France). The concentrated solar beam produces a focal spot, ca. 15 mm in diameter, with a

power density up to 16 MW/m2 [11]. Total incident radiation can be controlled by a shutter

positioned between the sun-following heliostat and the parabolic concentrator. Fig. 1a shows

the spherical quartz chamber used during the sintering process, which is receiving the solar

radiation that is concentrated at the parabolic reflector - partially seen- over the chamber. The

brown pellet was placed in a water cooled holder in order to prevent the overheating of the

specimen, Fig. 1b, with a thermocouple positioned at the rear surface of the specimens. To

avoid oxidation, before 10 min- and during the sintering process, Argon was flown through

the chamber. CSE sintering process was performed with a solar radiation of about 900-1000

W/cm2. Several trials were previously performed to obtain the adequate sintering, that

corresponded to a temperature of 750-800 C at the rear surface. Fig 1c shows a typical

temperature profile obtained with a solar radiation of 993 W/m2. Shutter was first open to

15% to pre-heat the sample up to 267 C, then opened to 25% to heat it up to 435 C and

finally the shutter was set to 45% to maintain the specimen at about 770 C for 30 minutes.

Microstructural and compositional analysis, were made using a JEOL J8M6500 Scanning

Electron Microscope and Energy Dispersive Spectroscopy (EDS), respectively. Porosity

measurements we calculated from the apparent density obtained according Archimedes

method with distilled water [5].

Results and Discussion

Green Ti pellets with nominal porosities of 60, 70 and 80% were produced using the space

holder powder metallurgy technique, Fig. 2a, with Ti powder and NaCl crystals. After dissolving

the NaCl space holder in hot water, brown Ti pellets were strong enough to be handled. At this

stage the brown pellets specimens revealed a uniform pore distribution as it can be seen in Fig

2b. After the sintering with CSE, Fig 2 c , at the naked eye, the specimens keep the porous

structure, show a good integrity with not apparent change in size.

Two sintered foams of 60, 70 and 80 % nominal porosity were measured by triplicate to

determine the total open porosity, Table 1. The final porosity was always slightly lower than

the estimated from the space-holder weight added during the green pellet preparation.

Nevertheless, in all cases the porosity is over the 50%, value considered as the minimum

required by the cortical bone to have suitable mechanical properties and osseointegration.

Therefore, the total open porosity achieved cover the target planned with a maximum porosity

achieved up to 77%. Recently Chen et al. [16] measured the mechanical properties of porous Ti

samples with porosities between 64 and 76% using liquid foaming technique with H2O2 as

foaming reagent. They reported a compressive strength and Young's modulus of 102 10 MPa

and 3.3 0.8 GPa respectively for a 64% porosity, and 23 10 MPa and 2.1 0.5 GPa for 76%

porosity, concluding its potential use for replacing cortical bone and tissue engineering

scaffolds respectively.

SEM images of 60, 70 and 80% nominal porosity CSE sintered Ti foams are presented in Fig. 3.

Low magnification images (Fig. 3 a, c, and d) showed the macropore size ranges from

approximately 500 to 1000 m, that correspond with the original size of the NaCl space holder

crystals. This indicates that there is no any collapse or significant reduction of the macropores

during the compaction, NaCl dissolution, or sintering process steps. Large pores (>300 m) are

critical for the direct osteogenesis in the implant by allowing vascularization [17]. In the high
magnification images (Fig 3 b, d and e) it can be observed the partial melting and sintering of

the Ti powders. For the three porosities evaluated, the macropore-wall structure is rough and

composed of sintered powders with a good metallurgical joining and a micro-scale pore sizes

in the range of 1-10 m. Micropores of this range of size have been reported as enhancing

structures for creating hypoxic conditions and induce osteochondral formation before

osteogenesis [16].

Conclusions

Concentrate Solar Energy heating appears to be an effective sintering process, in terms of

temperature and process time, when applied to the production of highly porous titanium

foams using the space holder technique. Titanium foams obtained showed a promising

macropore and micropore structure for tissue engineering scaffold and implants applications.

Acknowledgement

This work was supported by the Access to Research Infrastructures Activity in the 7th

Framework Program of the EU (SFERA Grant Agreement no. 228296) at the PROMESCNRS

Solar facility; and partially supported by the Ministry of Economy and Competitiveness through

the program MAT2013-48224-C2-1-R .

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 c) 900
Ti 80% porosity
800

700
Temperature (C)

600

500

400

300

200

100

0
0 500 1000 1500 2000 2500 3000 3500 4000
Time (s)

Fig 1. Parabolic solar concentrator a), detail of the sample inside the sintering chamber b) and
temperature measured during the sintering process of 80 % nominal porosity sample using a
solar radiation of 993 W/m2 c).

a) b) c)
Fig 2. Macroscopic view of the green pellet a), NaCl dissolved brown pellet b), and sintered Ti
foam c).

Fig 3. SEM images of CSE sintered Ti foams with nominal porosities of 60%, a) and b), 70%, c)
and d), and 80%, e) and f).

Table 1. Nominal and measured porosity of sintered Ti foams

Ti-foams Nominal porosity Measured porosity
(Green samples) (sintered samples)

60% vol 60 58.1 3.84 %

70% vol 70 64.4 3.57 %
80% Vol 80 77.2 1.52 %

Highlights

Porous Titanium foams sintered using sustainable Concentrated Solar Energy

Controlled open porosity and pore size by space holder powder metallurgy route
Promising pore structure for tissue engineering and implants applications