Accepted Manuscript

Ecological footprint of biomaterials for implant dentistry: is the metal-free practice

an eco-friendly shift?

Letícia S. De Bortoli, Luciana M. Schabbach, Márcio Celso Fredel, Dachamir

Hotza, Bruno Henriques

PII: S0959-6526(18)33905-2

DOI: 10.1016/j.jclepro.2018.12.189

Reference: JCLP 15247

To appear in: Journal of Cleaner Production

Received Date: 17 July 2018

Accepted Date: 18 December 2018

Please cite this article as: Letícia S. De Bortoli, Luciana M. Schabbach, Márcio Celso Fredel,
Dachamir Hotza, Bruno Henriques, Ecological footprint of biomaterials for implant dentistry: is the
metal-free practice an eco-friendly shift?, Journal of Cleaner Production (2018), doi: 10.1016/j.
jclepro.2018.12.189

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 ACCEPTED MANUSCRIPT

9129 words

ECOLOGICAL FOOTPRINT OF BIOMATERIALS FOR IMPLANT DENTISTRY:

IS THE METAL-FREE PRACTICE AN ECO-FRIENDLY SHIFT?

Letícia S. De Bortoli1, Luciana M. Schabbach1,2, Márcio Celso Fredel2, Dachamir Hotza2,3,

Bruno Henriques2,4,5

1Department of Engineering, Federal University of Santa Catarina (UFSC), Campus

Blumenau, 89036-002 Blumenau, SC, Brazil.

2Ceramic and Composite Materials Research Group (CERMAT), Mechanical Engineering

Department (EMC), Federal University of Santa Catarina, Campus Trindade, 88040-900
Florianópolis, SC, Brazil.

3Departmentof Chemical and Food Engineering (EQA), Federal University of Santa Catarina
(UFSC), Campus Trindade, 88040-900 Florianópolis, SC, Brazil.

4School of Dentistry (DODT), Postgraduate Program in Dentistry (PPGO), Federal University

of Santa Catarina, Campus Trindade, 88040-900, Florianópolis/SC, Brazil

5CMEMS-UMinho, University of Minho, Campus de Azurém, 4800-058 Guimarães, Portugal

Correspondence to: CERMAT – Ceramic and Composite Materials Research Group, Federal
University of Santa Catarina, Campus Trindade, 88040-900, Florianópolis/SC, Brazil.

E-mail address: luciana.maccarini@ufsc.br (Luciana M. Schabbach);

bruno.henriques@ufsc.br (Bruno Henriques)

Abstract. The enhanced aesthetic and biocompatibility features of ceramics over metals have
been driven implant dentistry to a metal-free practice. In this sense, the aim of this study was
to assess the sustainable potential of this migration. The main metallic and ceramic materials
used in implant dentistry were evaluated through a comparison of the carbon footprint,
embodied energy and water consumption related to their primary production and the
mechanical properties. The materials evaluated were: alumina (Al2O3), yttria-stabilized
tetragonal zirconia polycrystal (Y-TZP), stainless steel 316L (SS), cobalt chromium alloy
(CoCr), commercially pure (cp-Ti) titanium and alpha-beta titanium alloy (Ti6Al4V). A
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dedicated software for environmental impact assessment providing a materials properties

database was used in this analysis. The results showed that the primary production of ceramic
materials tends to have a less significant impact compared with metallic materials, with lower
values for the generation of greenhouse gas emissions, water consumption and embodied
energy. These results indicate that the migration currently seen in implant dentistry from using
metallic components to ceramic ones is positive from an environmental perspective.

Keywords: Carbon Footprint, Implant Dentistry, Metal alloys, Ceramics.

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1. INTRODUCTION

Concerns regarding environmental issues have boosted studies on the quantification of the
impacts generated by human activity, mainly in the production of consumer goods. In this
regard, the emergence of tools to assess environmental impacts linked to the process of
obtaining various products has driven many industrial manufacturers to focus on searching for
more efficient materials that are less aggressive toward the environment (Popovic et al., 2017).

The production of dental implants in the global scenario has experienced accelerated growth in
recent years. The advancement of this market is attributed to factors such as increased life
expectancy, in addition to increased incidence of dental caries and periodontal diseases,
resulting in greater demand for cosmetic and functional dentistry. According to the World
Health Organization, approximately 30% of people currently aged between 65-74 years have
no natural teeth (World Health Organization, 2012). Moreover, according to data from the
American Academy of Implant Dentistry, approximately 3 million Americans currently have
dental implants, and this number is growing at a rate of around 500 thousand each year. A
recent report by Research and Markets (Dental Implants Market By Material, Type, Structure
- Global Forecast to 2022) shows that Europe had the largest share in the global market for
dental implants in 2016, followed by North America, Pacific Asia and Latin America. The
report estimates that the global market for dental implants is expected to reach around USD
4.497 million by 2022, following a compound annual growth rate (CAGR) of 6.1% over the
forecast period of 2017 to 2022.

In Brazil, according to survey performed by the Federal Council of Dentistry (Conselho Federal
de Odontologia/CFO), approximately 800 thousand implants and 2.4 million dental prosthetic
components are fitted in patients every year (Viturino, 2014).

Thus, with the growth in the global market, the sector involved in the production of dental
implants and their components has a particular interest in issues involved in the processing of
the materials from which they are produced. This leads to the emergence of questions facing
the extraction of raw materials and the environmental impact, energy costs, water consumption
and emission of polluting gases associated with the production process, among other aspects.

A system of implant-supported dental rehabilitation (Figure 1) may consist of several

components including the dental restoration (single and multiple-unit crowns), the implant
abutments and the implant. Some of the main materials used for the production of these
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components are: stainless steel 316L, alumina (Al2O3), yttria-stabilized tetragonal zirconia
polycrystal (Y-TZP), cobalt-chromium alloy (CoCr), commercially pure (cp-Ti) titanium and
alpha-beta titanium alloy (Ti6Al4V), as shown in Figure 2 (Christensen and Ploeger, 2010;
Dubruille et al., 1999; Fabris et al., 2017a; Flamant et al., 2016; Henriques et al., 2013, 2012b,
2012a; Reveron et al., 2017). It is known that the production of these components requires
specific raw materials (e.g., of high purity), sophisticated manufacturing techniques and
accurate process control, in order to obtain the desired mechanical and aesthetical properties.
However, despite the consolidation of the processing techniques for these materials/products,
little is known about the environmental impact associated with their fabrication. In particular,
comparative analyses of similar materials available for a given application according to an
environmental impact perspective is currently lacking. In fact, to the best knowledge of the
authors and to the present date, no literature exists on this specific topic.

Figure 1 - Illustration of a dental implant-supported rehabilitation system with its components.

(Adapted from: pasquasouthdental.com).
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Figure 2 - Examples of prosthetic components produced with different materials (metals and
ceramics). Alumina crowns (Procera, Nobel Biocare); Stainless steel (Arcsys abutments,
FGM); Zirconia Y-TZP implants (Straumann); CP titanium implants (Straumann), Ti6Al4V
(Straumann abutments) and Co-Cr alloy (Straumann abutments) (source: adapted from
manufacturers catalogs and websites).

In this context, the ecological footprint can be regarded as a planning tool aimed at achieving
sustainability, which involves quantifying the impact of certain actions and productive
processes. According to Wackernagel and Rees (1996), the ecological footprint measures the
impact generated by a given population on nature, this being represented by the area of land
surface required to sustain the levels of resource consumption of this population. This
methodology considers, among other factors, the carbon footprint by quantifying the
greenhouse gas emissions, converted into CO2 equivalent, since oceans and forests absorb part
of the carbon dioxide. Currently, the carbon footprint is the most representative factor in the
calculation of the ecological footprint. Since the 1970s, industrial and technological
developments have led to greater emissions of polluting gases to the atmosphere during the life
cycle of a product, process or service. (Global Footprint Network, n.d.).

Within this scenario, a more complete evaluation can indicate the impact associated with each
processing stage in the production of a product or material, from the extraction of the raw
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materials to the final disposal of the product. This approach is called life cycle assessment
(LCA) (Bauer et al., 2008) and addresses the environmental impact during the life cycle of a
product, such as water consumption, emission of pollutants, energy expenditure, pollution of
rivers, climate change, depletion of mineral resources, fossil fuels and renewable energy
sources, among others. This technique is employed with the aim of quantifying environmental
impacts, both positive and negative, in order to enable comparative studies of different
materials available for a particular application (Hafner and Schäfer, 2018). The final aim of
LCA is to identify opportunities to reduce the overall environmental effects of the system under
study (Gloria, 2013).

According to Ashby (2012), as currently practiced, life cycle assessment can be expensive and
complex, requiring experts, demanding long time and resources, which in many cases does not
make it attractive for engineering design. One way to overcome those issues is to focus on
resource-energy consumption and -carbon dioxide emission. The CES Selector software
developed by Ashby and coworkers (Ashby, 2005) can provide these information about
materials, i.e. the energy spent and the CO2 released in their obtention.

The concept of carbon footprints, i.e. the mass of CO2 equivalent in kilograms (kg) produced
and released into the atmosphere as a consequence of the production of 1 kg of the material
(Ashby, 2012), can be used by companies to reduce exposure to carbon prices or highlight the
positive actions they have taken. The concept of a ‘footprint’ can be useful to promote the
implementation of local policies that help meet overarching national objectives and foment
responsible and sustainable consumption (Peters, 2010).

The analysis of the environmental impacts associated with the production of implantable
biomaterials represents a new scenario of research, establishing a new perspective of selection
of materials to be used in this area (Gouveia et al., 2017). In the framework of materials applied
to implant dentistry a trend toward the use of new ceramic components rather than metallic
ones has been observed, aiming at addressing enhanced aesthetic, strength and biocompatibility
requirements (Bona et al., 2015; Dantas et al., 2018; Denry and Kelly, 2008; Fabris et al.,
2017b, 2016; Gouveia et al., 2017; Henriques et al., 2017; Roedel et al., 2018; Santos et al.,
2016a; Santos et al., 2016b; Santos et al., 2016c; Sivaraman et al., 2018; Zhang and Kim, 2009).

The present study is aimed at evaluating the sustainability of primary production of the most
common biomaterials currently used in implant dentistry: stainless steel 316L, alumina
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(Al2O3), yttria-stabilized tetragonal zirconia polycrystal (Y-TZP), cobalt-chromium alloy

(CoCr), commercially pure titanium (cp-Ti) and alpha-beta titanium alloy (Ti6Al4V), by
comparison of the carbon footprint, embodied energy and water consumption related to their
primary production and mechanical properties.
The purpose is to establish a relationship between mechanical properties and the relative
environmental impact assessment in the materials selection, and to evaluate the migration trend
recently seen in implant dentistry from traditional metallic components to ceramic ones.
The paper here presented is structured as follows: the Material and Methods section addresses
the biological information and the typical mechanical properties of the selected biomaterials
(Section 2.1), as well as the details of the software used in this study, the CES Selector, which
is the main tool used for selection of materials and environmental impact assessment (Section
2.2). The results are then presented in Section 3. Afterwards, the carbon footprints vs.
mechanical properties charts are presented for the selected materials. In addition, in this
section, the analysis of the environmental impact associated with the primary production of the
selected biomaterials is also given.
Considering the current relevance of titanium (cp-Ti and Ti6Al4V) and zirconia in the implant
dentistry field, being the main competing materials, a comprehensive description of their
primary production industrial routes is then presented in Section 3.4. The environmental
impacts of the main manufacturing processes and materials primary production are briefly
presented Section 3.5.
Finally, the main conclusions of this study are drawn in Section 4.

2. MATERIALS AND METHODS

2.1. Selection of Biomedical Materials

The biomaterials used in this study were selected in order to allow a comparison between the
main metallic and ceramic materials currently employed for the production of implants and
dental prostheses. Six different biomaterials were analysed: alumina (Al2O3), yttria stabilized
tetragonal zirconia polycrystals (Y-TZP), stainless steel 316L, cobalt-chromium alloy (CoCr),
commercially pure titanium (cp-Ti), and alpha-beta titanium alloy (Ti6Al4V).

Alumina (Al2O3) is a highly inert material that is resistant to most corrosive environments and
physiological conditions, including human body fluids. It has high hardness and mechanical
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resistance, so it is widely used in biomedical applications. It is currently used in dentistry

mainly through the commercial system Procera AllCeram (Nobel Biocare) in the production of
dental crowns (Shenoy and Shenoy, 2010), as shown in Figure 2a.

Zirconia (ZrO2) is also classified as a bioceramic, with high chemical and mechanical
resistance, and high hardness (Özkurt and Kazazoğlu, 2011). This material is obtained from
zircon (ZrSiO4), requiring a significant amount of processing steps. Zirconia is a polymorphic
material with monoclinic, tetragonal and cubic forms. The monoclinic phase, which is stable
at room temperature, does not have the mechanical resistance necessary for dental application
and thus it must be stabilized in other phases. The tetragonal phase is more resistant and can
be obtained at room temperature after sintering, with the addition of small amounts of oxides
or dopants (such as yttria, Y2O3) to stabilize the tetragonal crystalline phase. This provides a
material suitable for the production of dental implants, abutments and restorations (Figure 2)
(Azevedo et al., 2008).

The austenitic stainless steel 316L offers sufficient resistance to corrosion for implantation in
the human body. This is due to the formation of a passive film resulting from the presence of
chromium in proportions higher than 11%, as well as to the presence of nickel, which stabilizes
the austenitic phase and increases the corrosion resistance of the material (Araújo and Couto,
2005). The application of stainless steel in implant dentistry is very low, although it may be
found in some prosthetic screws and abutments (Figure 2).

Commercially pure titanium (cp-Ti) is currently the most commonly used material for the
manufacture of dental implants, being used to produce the component directly implanted, i.e.,
in contact with the bone. Properties such as high biocompatibility, low density, high corrosion
resistance and mechanical strength make this material one of the most appropriate and viable
among the options currently available for dental implants (Figure 2) and orthognathic surgery
(Torres et al., 2007).

The alpha-beta titanium alloy (Ti6Al4V) has excellent mechanical properties when compared
to cp-Ti, resulting from the stabilization of the alpha phase by aluminum and the beta phase by
vanadium, both phases being present at room temperature. This stabilization of the phases leads
to an increase in the fracture resistance and hardness of this alloy, providing almost twice the
tensile strength of cp-Ti. It is used for the production of the majority of abutments due to their
slender shape (Figure 2), which requires stronger alloys in order to cope with occlusal loads
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(Bauer, 2007).

Finally, a cobalt chromium alloy (CoCr) was also included in this study. This alloy contains
cobalt (Co) as the main component, with at least 25wt% chromium (Cr) and less than 4 wt%
molybdenum (Mo). CoCr features high tensile strength, high wear resistance, excellent
corrosion resistance and high hardness, allowing its use in dental prosthetic components such
as metal-ceramic dental restorations, substructures, crews and abutments (Figure 2). Among
these, it is mainly applied in infrastructures of implant-supported fixed partial prostheses
(Martinelli, 2016).

2.2. Tools for Selection of Materials and Environmental Impact Assessment

The construction of property maps allows the designer to evaluate each material within a class,
with respect to its characteristics and specific properties, commonly making comparisons in
groups of two, especially in the area of materials science and engineering. This makes it
possible to establish sequential comparisons and then select the most appropriate material for
a given application (Morini et al., 2016). Aspects such as production costs and environmental
impact can also be included. In this approach, the materials suitable for a particular application
are arranged in a hierarchical manner allowing the best option to be identified.

Several software are available for this type of analysis and the selection of materials. One
example is the CES Selector (based on the Cambridge Engineering Selector approach)
developed by Ashby and coworkers (Ashby, 2005), which provides a database with technical
information on more than 4000 different materials. For each material, the physical, mechanical,
thermal and electrical properties are available along with potential applications in
manufacturing processes and data on global production, market value, production of CO2 and
embodied energy (Morini et al., 2016).

In CES Selector, based on the property maps of materials, through the intersection of
information related to material in a database with incremental steps of restrictions, the materials
that match the requirements of a certain project can be found (Ashby, 2005). Based on this
information it is possible to generate graphs and maps that facilitate the analysis and
visualization of the data. The software also presents an audit module for eco-sustainability (Eco
Audit), in order to assess the environmental impacts of the processes and products. Thus, this
is a tool that allows the application of a development strategy with sequential design, the
efficient and quick selection of materials, and also the evaluation of environmental impacts
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through the definition of the desired characteristics and restrictions relating to the project
(material or product) development. (Birch et al., 2010).

Regarding the environmental impact assessment, there are various software packages used as
LCA tools (e.g. IDEMAT, SimaPro, and GaBi) (Raoufi et al, 2017). The CES Selector software
stands out as a tool that allows a quick and relatively simple analysis of the impact of materials
production (carbon footprint, embodied energy and water use), thus enabling extremely useful
comparative analyses for the design/selection of materials. On the other hand, more specific
software programs are also available for LCA (e.g. SimaPro), allowing to perform more
complete and complex analyses often conducted by expert users but demanding long time and
specific information that are not easily accessible.

In this study, the current migration from metallic to ceramic components, within the frame of
a "metal-free" practice, seen at the implant dentistry is analysed from an environmental
perspective. To perform this study, the data available in the database of the commercial
software CES Selector (Granta Design, Cambridge, UK), version 2014, was used as well as the
ECO-Audit module. The comparative study of the materials, the carbon footprint, embodied
energy and water use in their primary production were conducted. In addition, some of the
physical and mechanical properties of the materials evaluated (Table 1) were also obtained
from CES Selector database.

The CES Selector assigns values to the carbon footprint associated with the primary
production of each material present in the database. The CO2 footprint of primary production
represents the mass of greenhouse gases (CO2 equivalent) in kilograms (kg) produced and
released into the atmosphere as a consequence of the production of 1 kg of the material (Ashby,
2012). The values for the CO2 footprint of the primary production of metallic materials
represent the production of ingots while for ceramic materials the values refer to the production
of sintered parts obtained by simple molding. (Granta Design Limited, 2014). The carbon
footprint of the primary production of these materials can thus be calculated from the ratio
between the sum of the mass of CO2 emitted by the production plant of the material during one
year and the total mass of material produced in the same period of time (in kg/kg).

Besides the data related to the carbon footprint, the software also provides the energy
consumption of primary production associated with obtaining 1 kg of material, i.e., the costs
involved in extracting the raw materials, processing it and manufacturing the ingots (metals)
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or sintered parts (ceramics). The embodied energy per unit of weight of material produced is
calculated considering the ratio between the total energy input of the production plant in one
year and the mass of material produced in the same period (in MJ/kg).

The water consumption is determined through direct measurements of factory inputs and
outputs (in l/kg, that is, liters of water per kilograms of material produced).

It should be noted that the range of values estimated by the CES Selector software is based on
the literature. However, the CO2 emissions, energy requirements and water consumption may
vary according to the different types of processes employed in each plant production, and the
values obtained can show a variation of up to 20%. Thus, when comparing materials,
differences of less than 20% are not usually significant (Granta Design Limited, 2014).

3. RESULTS AND DISCUSSION

3.1. Mechanical Properties and Biocompatibility

The selection of materials for the production of implants and dental prostheses requires a
careful analysis of their mechanical behavior in order to identify those that best suit the
conditions imposed by the body. Thus, they need to be elastically compatible with human bone,
resistant to the intraoral environment and support the mechanical loads present during
mastication. In Table 1, the average values for the main mechanical properties of the materials
selected for this study are presented. This information was taken from the database of the CES
Selector software. The term bioceramic is used in the software to refer to the class of materials
dedicated to biomedical applications, e.g., zirconia bioceramic refers to zirconia stabilized with
yttria (Y-TZP) and alumina bioceramic refers to alumina (Al2O3).

The Young’s modulus is an important parameter in the case of materials for implants and the
appropriate value is dependent on the place where these materials will be applied. A material
used in a dental implant should have a value comparable to the Young’s modulus of human
bone, which is approximately between 15 and 30 GPa (Griggs, 2017). Conversely, for
applications in abutments and crowns (dental prostheses), a high value is desirable. Materials
with an elastic modulus that is much higher than that of the bone will produce a severe elastic
mismatch between the implant and the adjacent bone, which may favour the stress-shielding
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phenomenon. On the other hand, for dental prostheses applications, materials with higher
elastic modulus have therefore greater stiffness, thus allowing the production of thinner
prostheses.

Table 1 - Mechanical properties of bone and some materials used in dental implants. (Data
obtained from data Granta Design Limited, 2014).

Young's Vickers Flexural

Density
Material Modulus Hardness Strength
(Mg/m³)
(GPa) (VH) (MPa)

Stainless steel, austenitic,

7.87 - 8.07 190 – 205 170 - 220 170 - 310
AISI 316L

Titanium, commercially
4.54 - 4.55 105 - 120 104 - 105 310 - 400
pure (cp-Ti), Grade 4

Titanium, alpha-beta alloy,

Ti-6Al-4V 4.41 - 4.45 110 - 119 337 - 373 786 - 1080

Cobalt-base superalloy,
8.28 - 8.3 235 - 247 260 - 310 512 - 590
CoCr

Zirconia, bioceramic (Y-

5.85 - 5.9 205 - 212 1200 - 1250 850 - 910
TZP)

Alumina, bioceramic
3.93 - 3.98 380 - 400 1960 - 2300 540 - 560
(Al2O3)

Bone 1.8 – 2.1 17 - 22 20 - 40 150 - 200

Based on the data presented in Table 1 and considering the fact that the flexural strength of
human bone typically varies between 135-193 MPa, it can be seen that all these materials
exhibit a flexural strength higher than that of human bone. High-density materials result in
heavier implants and prostheses and the patient may experience discomfort and adaptation
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difficulties. Thus, materials that associate low density and high strength are preferable to other
options.

In addition to the mechanical compatibility, the production of substances through the

interaction of the implants with the oral cavity is dependent on a complex chemical-physical
balance of the various component materials of the implant (Martinez Olmedo et al., 2017), and
so all components must have properties compatible with insertion in the human body. The oral
cavity is an extremely corrosive environment with a high concentration of minerals and salts.
A study on the fracture patterns of implants and prosthetic screws submitted to cyclic loads
shows that the biological environment promotes the extension of existing microcracks on the
titanium surface. Thus, the concentration of enzymes and direct interaction with the cells and
proteins present in saliva can significantly affect the implant surface (Elias, 2012).

The components produced using cp-Ti and Y-TZP both showed excellent biocompatibility
since they were bio-inert, i.e., they did not promote any chemical reaction between the tissue
and the implant (Saini, 2015).

The biocompatibility of cp-Ti is due to the spontaneous formation of an inert surface layer of
titanium oxide, which is a passive corrosion film inhibitor. This characteristic, coupled with
low density, makes titanium an ideal material for applications in the human body (M.
Ramazanoglu and Oshida, 2011). However, in order to obtain a material that meets higher
mechanical requirements, 6% of aluminum and 4% of vanadium were incorporated into the
titanium, leading to the TiAl6V4 alloy. However, it should be noted that studies indicate that
small concentrations of aluminum and vanadium are released in the human body and both of
these metals are toxic (Joseph et al., 2009).

Metallic implants release metal ions when placed in the electrolytic environment of the human
body. Some of the metal ions originating from implants and their wear residues remain in the
local tissues while others may attach to proteins that are then taken through the bloodstream
and lymphatic system to remote areas (Joseph et al., 2009).

Concerns regarding the biological responses to the release of metal ions along with aesthetic
issues have boosted the search for "metal-free" materials for prosthetic applications. In this
context, the stabilized tetragonal form of zirconia has become the main material used to replace
traditional metallic materials in dental prosthetic systems (Tanimoto, 2015).
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3.2. Carbon Footprint vs. Mechanical Properties

3.2.1 Flexural Strength

In this study, the flexural strength was the parameter used to assess the mechanical resistance
of the materials for application in dental prosthetic applications, since this represents one of the
key requirements for determining the quality and service life of dental materials used in load
bearing applications. Prostheses and dental implants are constantly subjected to shear strain
from the action of chewing, as well as the static strains arising from tensile stress in the gingival
portion of the pontics in implants, and compressive stress, which occurs in the occlusal portion
of the prosthesis (Caputo and Standlee, 1987). According to Anusavice et al. (1985), the
bending stress is the main mechanical stress imposed on a dental prosthesis during its clinical
use, and thus this is the most important mechanical parameter for evaluation.

Figure 3 shows the carbon footprint values (primary production) plotted against the flexural
strength for the biomedical materials selected for this study. Typical bone flexural strength
values were also plotted for comparison. It gets evident that the zirconia bioceramic (Y-TZP)
offers the best relation between carbon footprint and flexural strength, providing high strength
at a low environmental cost. Also, the metallic materials analyzed tend to present higher values
for environmental impact (emission of CO2 during their primary production).

In addition to the flexural strength, the elastic modulus of materials is an important mechanical
property to be considered in the selection and application of the biomedical materials
considered in this study. The elastic modulus must be higher than that of human bone (15-30
GPa) to withstand the strains imposed on them (Griggs, 2017). A high elastic modulus ensures
a lower degree of deformation of the material. However, as mentioned above, the
compatibility/similarity of the mechanical response of the materials that make up the
mechanical unit must be established. An incompatibility of the modulus values can result in
failure of the material due to the stress-shielding effect, i.e., an imbalance of normal stresses
applied on the bone, since, under strain, components with very different elastic modulus have
distinct responses, resulting in overloading in some areas and lack of load in others (Didier et
al., 2017).
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Figure 3 - Comparison between the human bone and the main biomedical materials used in
prosthetic dentistry with regard to the flexural strength and carbon footprint of primary
production. (Data source: CES Selector software, Granta Design Limited, 2014).

3.2.2 Young's Modulus

Figure 4 shows the carbon footprint values of primary production plotted against the Young's
modulus values for the main biomedical materials used in implant dentistry. It should be noted
that although alumina displays low carbon footprint values, the Young's modulus is very high
when compared to human bone. Materials with a moderate Young's modulus (i.e., similar to
that of the bone), which minimizes the stress-shielding effect, are the most desirable. In this
case, the zirconia bioceramic (Y-TZP) presents the most attractive combination between
carbon footprint and Young's modulus when compared to other materials in analyzis.
Commercially pure titanium (cp-Ti) and the alpha-beta titanium alloy (Ti6Al4V), despite
offering a more attractive Young's modulus, have a high environmental impact (the CO2
footprint for zirconia is around 5 kg/kg while for cp-Ti and Ti6Al4V it is around 50 kg/kg).
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Figure 4 - Comparison between human bone and the main biomedical materials used in implant
dentistry with regard to the Young's Modulus and carbon footprint of primary production. (Data
Source: CES Selector software, Granta Design Limited, 2014).

3.2.3 Hardness

The hardness of the material that constitutes the implant is also an important mechanical
property as it is related to the dimensional stability of the piece under the stress applied during
its service life. A material of low hardness may undergo undesirable deformation and
consequently reduce the quality of the implant and/or hinder its applicability. Figure 5 shows
the relationship between the carbon footprint and Vickers hardness for the six materials studied,
including the hardness of human bone.
The data in Figure 5 shows, as expected, that ceramic materials present greater Vickers
hardness than metallic materials. Alumina has the highest hardness values and it should be
noted that very high values can influence the final processing of the workpiece, requiring larger
amounts of energy for machining and polishing, making the process less economical and
increasing the environmental impact (Grzesik et al., 2016). Based on these considerations and
the data in Figure 5, zirconia (Y-TZP) appears to offer the best combination of characteristics,
with a low carbon footprint and adequate hardness.
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Figure 5 - Comparison between human bone and the biomedical materials used in implant
dentistry with regard to Vickers Hardness and carbon footprint of primary production. (Data
source: CES Selector software, Granta Design Limited, 2014).

3.3. Environmental Impact Associated with the Primary Production

Based on the data provided by the software CES Selector, the average impact associated with
the primary production of each material was estimated, considering the carbon footprint, water
usage and energy consumption. The results obtained are reported in Figure 6. It should be noted
that the values for the CO2 footprint (kg/kg), water usage (l/kg) and embodied energy (MJ/kg)
of the primary production of the materials provided by the software are related to the production
of ingots for metallic materials and sintered parts obtained by simple molding in the case of
ceramic materials. In this way, only the primary production of the different biomedical
materials is evaluated in this analysis of environmental impact, with the impacts of specific
production and processing steps (e.g. machining, powder injection molding, physical and
chemical surface treatments, etc.) of the final components being neglected in this study and
thus consisting of a limitation of the same.
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685.5
577
531.5
223.5

190.5

197
100.85

108.5
89.5
58.55

49.05

39.05
52.1

46.4
11.9
6.26
4.83
2.81

ALUMINA BIO- ZIRCONIA STAINLESS CO-CR TITANIUM TI6AL4V

CERAMIC BIO-CERAMIC STEEL 316L ALLOY CP ALLOY

CO2 Footprint (kg/kg) Water usage (l/kg) Embodied energy (MJ/kg)

Figure 6 - Comparative analysis of environmental impact of primary production of selected

materials: carbon footprint, water usage and energy consumption. (Data source: CES Selector
software, Granta Design Limited, 2014).

On analysing the carbon footprint of the materials separately, it can be observed that the
alumina bioceramic has a tendency to present a lower impact, with an average value of 2.81 kg
of carbon dioxide equivalent emitted for every 1 kg of material produced. Compared with the
alumina bioceramic, the carbon footprint of the zirconia bioceramic is 72% higher, that for the
stainless steel is around 123% higher and the value for the cobalt chromium alloy (CoCr) is
324% higher. The differences between the materials are even greater when the CO2 emission
in the primary production is considered with cp-Ti and Ti6Al4V having values 1290% and
1550% higher, respectively, in comparison with the alumina bioceramic.

The zirconia bioceramic and titanium alloy have the highest flexural strength values, as seen
in Figure 3 and Table 1. The high strength and biocompatibility of these materials made them
highly appropriate for application in dental implants (they are currently the most used). The
data show that the carbon footprint for primary production of the zirconia bioceramic is 860%
lower than that of the titanium alloy (Ti6Al4V), with the production of the latter being more
harmful toward the environment.
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Currently, dental implants available on the market are mostly composed of two components,
an abutment produced with the Ti6Al4V alloy and a body directly implanted into the bone,
which is made of cp-Ti (Figure 1). However, the trend toward replacing metal components by
ceramic materials has promoted the development of dental implants made entirely of zirconia
Y-TZP, i.e., as a single body. The metal-free approach can also lead to better aesthetic
outcomes, since the appearance of ceramics can better mimic that of the natural teeth.
(Tanimoto, 2015). In addition, the better chemical resistance to corrosion, thermal stability and
good mechanical properties (resistance to wear and hardness) make ceramics, such as the Y-
TZP zirconia, increasingly attractive for implant dentistry (Azevedo et al., 2008; Saini, 2015).

3.4. Primary Production of Titanium and Zirconia

As stated before, the main materials currently used in the production of dental implants are
titanium (cp-Ti and Ti6Al4V) and zirconia (Y-TZP), with these materials being currently in
direct competition to get the title of the best material for implants. The data show a tendency
for the primary production of cp-Ti and Ti6Al4V alloy to have more significant environmental
impacts, since larger quantities of water and energy are required and larger carbon footprints
are displayed (Figure 6).

Currently, the largest fraction of the global production of metallic titanium ore originates from
ilmenite (FeTiO3), through the application of the Kroll process, where the ilmenite is combined
with coke and chlorine in a fluidized bed reactor at 1000°C, to produce titanium tetrachloride
(TiCl4). This, in turn, is purified through a continuous process of fractional distillation carried
out at 900 °C with magnesium casting and in a controlled atmosphere. The metallic titanium
sponge obtained from this process is shown in Figure 7. For the manufacture of ingots, the
metallic titanium sponge is initially crushed then undergoes a process of consumable-electrode
vacuum arc melting at extremely high temperatures (1600ºC) (Kroll, 1940). Therefore, the
various steps required and the complexity of the productive process (reaction in fluidized bed,
fractional distillation, vacuum arc melting), as well as the high temperatures employed, explain
the significantly higher values for the CO2 footprint. The water use and embodied energy
associated with cp-Ti are shown in Figure 6. It should be noted that the high values for the CO2
footprint associated with the production of cp-Ti is also strongly associated with the occupation
of the mining site, especially in cases where the law does not require the remediation of the
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soil, and the release of CO/CO2 after the initial chlorination process (Bordbar et al., 2017).

The production of the titanium alloy Ti-6Al-4V has a higher environmental impact compared
to cp-Ti because it involves the obtainment of the alloy elements (aluminum and vanadium),
in addition to the process of vacuum arc melting, where the crushed titanium sponge and the
alloy elements are melted in a chamber. This process starts with a first electrode of molten
mass, consisting of mechanically compressed blocks of sponge and alloy elements. The process
is conducted in a metallurgical vacuum, where the combination of alloy elements and titanium
takes place through the application of a direct current to create the electric arc between the
electrode and the alloy. This process forms a continuous molten mass of Ti-6Al-4V (Lütjering,
G.; Williams, 2003).

The minimization of segregate elements and a proper microstructure of the final material is
ensured through rigid control of the solidification of the alloy and formation of ingots
(Shackelford, 2005). The minimization of segregate elements and a proper microstructure of
the final material is ensured through rigid control of the solidification of the alloy and formation
of ingots [37]. The higher energy consumption associated with the production of CP titanium
and Ti-6Al-4V when compared to that of the zirconia bioceramic can be attributed to the need
for processes that require very high temperatures as well as two or three processes of vacuum
arc remelting, to ensure a purer and/or uniform composition. In Figure 7 the main steps
involved in the primary production of the cp-Ti and the Ti-6Al-4V alloy are shown.
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Figure 7 - Flowchart of production route of pure metallic titanium (cp-Ti) and Ti-6Al-4V
ingots. (Figure source: created by the authors)

In the case of the zirconia bioceramic, i.e., yttria-stabilized tetragonal zirconia polycrystal (Y-
TZP), the sources of the raw materials used industrially for the synthesis of zirconia (zirconium
dioxide, ZrO2) are minerals such as baddeleyite (ZrO2, less common) and zircon (ZrSiO4, more
abundant), requiring a chemical process of electrofusion. The extraction of raw material usually
occurs through the collection of sand and gravel, which contain zircon (ZrSiO4) mixed with
silicate, ilmenite (FeTiO2) and rutile (TiO2), from coastal waters. After the purification,
magnetic and electrostatic separators remove the ilmenite and rutile. All by-products of the
zircon purification/refining process are natural constituents of the sand and, therefore, are
typically discarded back into the water, at the extraction site, without harming the environment
(Allison, 2016). Yttrium oxide is added to obtain Y-TZP zirconia, which facilitates the
application of zirconia by achieving the desired mechanical properties (Mitchell and Heuer,
2005).

Figure 8 shows a schematic diagram of the process applied to obtain zirconia powder (Y-TZP),
involving a purification step, acid leaching, stabilization, precipitation and calcination. The
calcination step has the greatest impact on the energetic consumption of the process.
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The industrial routes used to obtain cp-Ti and zirconia (Y-TZP) both require the application of
chemical processes (caustic fusion and acid leaching to obtain zirconia Y-TZP and fluidized-
bed reaction with carbon and chlorination for cp-Ti). However, the production of pure titanium
and, more notably, the Ti-6Al-4V alloy requires more complex processes and relatively higher
temperatures, associated with very high energy consumption. Moreover, as mentioned
previously, the environmental impact related to the extraction of titanium and its processing
can be considerable, especially in cases where the law does not require the remediation of the
soil, which increases the carbon footprint associated with the primary production of this
material.

Conversely, for the production of zirconia Y-TZP, the chemical processes applied involves a
first step of caustic fusion of zircon (ZrSiO4) to obtain ZrOCl2 (Reed, 1995), and, another step
is relatively simpler, involving aqueous solution and precipitation (ALB Materials Inc). In
Figure 8 the main steps for obtaining the zirconia powder Y-TZP are shown. However,
subsequent steps are required to obtain simple molding/sintered parts (as referred to in the data
provided by the CES Selector software) and these are not shown in this flowchart.

In general, a pre-sintered block is obtained from the zirconia Y-TZP powder by cold isostatic
pressing, from which the shape of the dental component is obtained by CAD/CAM. This
component is then subjected to the final sintering process for densification and to obtain the
desired mechanical properties. Another important aspect to be considered is the fact that,
currently, in the production of implantable zirconia Y-TZP components, there is great concern
regarding the reuse of waste from the machining process (CAD/CAM) and studies indicate the
possibility of the recycling/reuse of these residues in the production of other products (Gouveia
et al., 2017). This is, certainly, another positive aspect to be considered in the current trend of
migrating from metal implantable components to metal-free ones.
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Figure 8 - Flowchart of production route to obtain stabilized zirconia powder (Figure source:
created by the authors)

3.5. Primary production and Manufacturing Processes in LCA

The manufacturing processes of implants, abutments and restorations involve mainly CNC
machining processes such as milling, turning and drilling (Araujo and Fromentin, 2017; Babík
et al., 2017; Belli et al., 2016; Bosch et al., 2014; Chen et al., 2014; Gouveia et al., 2017; Preis
et al., 2017; Santos et al., 2016c). A CNC-based machining system consists of machine tools,
fixtures, cutting tools, and work pieces, etc. As for carbon emissions of such a system, they are
often generated indirectly from operations of machine tools. For example, a machine tool is
powered up by electricity. The use of electricity for operations of the tool does not produce
carbon emissions; but the generation of the amount of electricity through power plants does (Li
et al., 2013).

The energy consumption of these processes, along with other metal cutting processes, is
estimated to be 50% higher than the consumption by using the forming methods such as
forging, casting and so on (Fritz, 2012). Dental implants produced by Ceramic Injection
Molding (CIM), seeking higher production at a lower cost, are now being explored
(Stanimirović and Stanimirović, 1999; Yang and Yen Chen, 2016). Attempts on metallic
implants production through Metal Injection Molding (MIM) has also been reported (Ferreira
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et al., 2016).

Regardless of the type of manufacturing process, the raw material extraction has been reported
to have the major environmental impact on the LCA of manufactured products, often exceeding
90% of the share (Ibbotson and Kara, 2014, 2013; Klocke et al., 2012) . This fact further
reinforces the outcomes of the preset study, where, due to the lack of specific data on
manufacturing processes, only the materials primary production was taken in consideration for
the assessment of the environmental impact.

4. CONCLUSIONS

The need to determine the environmental impact resulting from the production of materials is
becoming increasingly widespread and demanded with expansion of regulatory certifications
and the development of analysis tools aimed at sustainable development.

The impact associated with the primary production of six different biomedical materials most
commonly used in production of components applied to implant dentistry was assessed. It was
verified that ceramic materials tend display less environmental impact, generating fewer
emissions of greenhouse gases (GHGs) and consuming lower amounts of water and energy,
when compared to metals. Thus, the current migration from metal components to ‘metal-free’
materials can be considered positive from an environmental standpoint.

Considering the results obtained for the relationship between the mechanical property of
flexural strength and the carbon footprint, the zirconia bioceramic (Y-TZP) appears to be the
most eco-friendly material for the production of dental implants. Its emissions of GHGs (CO2
equivalent) is approximately 860% lower compared to the titanium alloy Ti6Al4V, which was
shown to have similar flexural strength.

This study stands out as the first attempt to assess and compare the environmental impact
associated with the production of biomedical materials used in implant dentistry. At this stage,
a stricted and preliminary analysis of the materials primary production was carried out, and
some issues arising from the components production and finishing process (e.g. machining,
powder injection moulding, finishing, among others) were not considered here and should be
addressed in further and complementary investigations.

The continuation of this research should be aimed at the development of a complete approach
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to assessing the environmental impact of the production processes, as foreseen in the LCA
methodology, including an analysis of the component processing steps, in order to proceed
with the identification of more environmentally friendly materials to be applied in implant
dentistry.

Acknowledgements

The authors would like to acknowledge the financial support provided by Capes and CNPq,
Ministry of Science, Technology and Innovation, Brazil. Project: PVE/CAPES/CNPq
407035/2013-3. Additionally, this work was supported by FCT (Portugal) with the reference
project UID/EEA/04436/2013, by FEDER funds through the COMPETE 2020 – Programa
Operacional Competitividade e Internacionalização (POCI) with the reference project POCI-
01-0145-FEDER-006941 and by the projects NORTE-01-0145-FEDER-000018-HAMaBICo
and FCT/02/SAICT/2017/3103-LaserMULTICER.

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ECOLOGICAL FOOTPRINT OF BIOMATERIALS FOR IMPLANT DENTISTRY:

IS THE METAL-FREE PRACTICE AN ECO-FRIENDLY SHIFT?

Highlights

 There is tendency to use new bioceramic components rather than metallic components
 Environmental impacts associated at production of biomaterials is a new approach
 Properties of metallic and ceramic materials used in implant dentistry are compared
 Carbon footprint, embodied energy and water consumption are preliminarily estimated
 Results show that the migration to "metal-free" devices is environmentally positive