j m a t e r r e s t e c h n o l .

2 0 1 9;8(5):4956–4964

Available online at [Link]

[Link]

Review Article

Zirconia in dental prosthetics: a literature review

Jonathan Grech, Elsa Antunes ∗

College of Science and Engineering, James Cook University, Townsville, QLD 4811, Australia

a r t i c l e i n f o a b s t r a c t

Article history: A large portion of the global human population carries a type of medical implant. Dental
Received 15 January 2019 implants are an important part of this category, and the crowns they support are vital for sat-
Accepted 26 June 2019 isfying the patients’ needs both functionally and aesthetically. Materials science pertaining
Available online 17 August 2019 to dental crowns is a driver of their development, and currently zirconium oxide (zirconia)
is a promising non-metal alternative, exhibiting biocompatibility and excellent mechanical
Keywords: and aesthetic properties. This review aims to collate a selection of the extensive testing and
3Y-TZP research that has been performed and evaluated on a variety of zirconia-based ceramics, as
Dental materials there are many commercial brands developing blank and powdered samples for refinement
Manufacturing technologies into structurally sound dental prosthetics. Significant advancements regarding manufactur-
Prosthetics ing technologies for zirconia-based ceramics are also currently in progress. Methodologies
Sintering and conditions for uniaxial and isostatic pressing of zirconia powder are reviewed, as are the
benefits of emerging CAD/CAM technologies. Several knowledge gaps were identified based
on this review, primarily that different sintering conditions and methodologies, such as
two-step sintering, should be investigated experimentally. Preliminary studies using alter-
native methods show promising results, and further trialling would help to ensure that
the mechanical, aesthetic and ageing properties of the final product are enhanced and
optimised.
© 2019 The Authors. Published by Elsevier B.V. This is an open access article under the
CC BY-NC-ND license ([Link]

Elsa Antunes obtained her PhD degree in Chemical Engineer-

ing from James Cook University in 2017. Elsa’s PhD was focused 1. Significance of biomedical implants
on understanding the impact of microwave pyrolysis condi-
tions on biochar properties produced from diverse biomass When the term biomedical implant is used, it is generally
sources. In 2018, she joined James Cook University as a Lec-
referring to a device used to support or replace a fraction of the
turer in Mechanical Engineering. She is currently focused in
whole biological structure [1], either for short or long-term use.
materials engineering, such as biomedical implants, transpar-
ent ceramics and surface functionality of biochar for water Procedures involving such implantations are common, with
purification, resource recovery and desalination. millions of patients undertaking them each year to improve
their quality of life [1]. In fact, experts estimate that 1 in 17
people in industrialised countries carry an implanted device
of some form [2,3]. The past six decades have seen major
∗
Corresponding author. advancements in the areas of microelectronics, biotechnology,
E-mail: elsa.antunes1@[Link] (E. Antunes). and materials science [3]. This has facilitated rapid develop-
[Link]
2238-7854/© 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
[Link]/licenses/by-nc-nd/4.0/).
 j m a t e r r e s t e c h n o l . 2 0 1 9;8(5):4956–4964 4957

ment of implant technologies in all medical fields, for example as gingivitis, which is an inflammation of the gingival com-
in the areas of orthopaedics, dentistry, and ophthalmic and plex, will cause sensitivity, swelling and pain in the gums. If
cardiovascular health [1]. left untreated, it will begin to affect the underlying bone and
can eventually cause the teeth to loosen, a condition known as
1.1. ARGMD classifications periodontitis [6]. Conditions such as the two aforementioned
are common, and the percentage of population with decayed
The extent to which a medical device is relied upon by its or missing teeth is particularly high in Australia [7]. Fractures
carrier for supporting or sustaining life varies depending on of the teeth due to events such as force of collisions may also
its purpose. The Australian Regulatory Guidelines for Medical cause pain because of the exposure and displacement of the
Devices (ARGMD), administered by the Australian Government tooth’s soft inner tissue known as the dental pulp [8]. There-
Department of Therapeutic Good Administration, categorises fore, it is apparent that in the structural restoration of the
medical devices into three major classes (I, II or III). This is to tooth via artificial implantation, prosthodontics also aims to
ensure that these devices are regulated in accordance with the alleviate pain and discomfort for the patient.
risks they pose individually [4]. To compound the physical pain caused by gum disease and
Class I devices are considered low to medium risk in terms tooth loss, the ability for patients to perform some everyday
of the potential for harm to be inflicted on the patient [4]. They activities is often also compromised. A 2012 study was con-
are generally not intended to sustain life, are non-medical and ducted to compare the production of certain speech sounds by
usually for transient (less than 60 min) or short-term use. They patients with and without anterior teeth [9]. One conclusion
are also non-invasive, meaning they either do not touch the of these studies was that the use of partial dental prostheses
skin or only contact intact skin. Examples of Class I devices was beneficial in improving speech [9]. Dental prosthetics also
include plaster or elastic bandages and non-sterile dressings make it easier for patients with gum diseases to eat without
[1,4]. feeling excessive pain, by filling the gaps where teeth have
Class II devices present a risk level ranging from medium fallen out and protecting the inflamed gums as the patient
to high [4]. They can be invasive, meaning the device pene- chews. These are evidence to suggest that prosthodontics also
trates the body through an orifice or is inserted during surgery. allows patients suffering tooth loss to live a more functional
They are non-active (do not require a power source), and are life.
usually for short term use with the exception of implants in In advanced stages of a periodontal disease, the supporting
the oral or nasal cavities and the ear canal, as these are often bone and tissue are destroyed, and plaque and tartar build-
long-term. Examples of Class II devices include contact lenses, up cause the gums to swell and pull away from the tooth.
implantable joint replacements, and dental prostheses such This causes pockets between the gum and the teeth, and
as bridges and crowns [4]. the presence of bacteria that inhabit this space causes an
Class III devices are considered to impose a high level of risk often-powerful odour to be expelled into the mouth. This is
of harm on patients [4]. These devices/implants are usually especially severe if the cavity is not sealed well from the mouth
invasive, and are generally required for applications involv- air [10]. Conditions with these symptoms will also leave a foul
ing the circulatory and central nervous systems. This means taste in the patient’s mouth. These symptoms are often awk-
they are most commonly for long-term use; however, Class III ward and embarrassing for patients during social interactions.
devices can also be transient/short-term depending on factors Properly installed dental implants for the treatment of such
such as whether it is to be absorbed by the body, and whether conditions are also an established way to restore confidence
it is intended to cause biological change. Examples of Class III for the patient in their social endeavours.
devices include absorbable sutures, cardiovascular catheters The final factor that motivates patients to seek prosthodon-
and antibiotic bone cements [4]. tic help is the desire to improve appearance. Missing teeth,
especially the more visible incisors and canines, is widely per-
1.2. Drivers for development in prosthodontics ceived as being aesthetically unappealing. A study conducted
by the University of Groningen Dental School evaluated the
Most dental prosthetics are Class II devices according to personal aesthetic perceptions of 74 patients with varying
the ARGMD as they are usually non-active but invasive and degrees of teeth missing (e.g. incisors, pre-molars, etc.) against
intended for long-term use [4]. Prosthodontics is a specialised patients with a natural dentition. In terms of positive feelings,
branch of dentistry that focusses on the design, manufacture on a scale of 0–5 (0 being feelings not present, and 5 being
and fitting of these artificial replacements for teeth, as well feelings strongly present), the average score by those missing
as restorations of natural teeth. This field of dentistry holds incisors was 1.0. This was compared to an average of 2.6 by
great significance as there is often a fine line between patient those missing no teeth [11]. Whilst this study was conducted
satisfaction and dissatisfaction due to the precision required in 1989, it can be assumed that with the increased levels of
for the prostheses. Nevertheless, it is understood that the employment competitiveness as well as the greater emphasis
patients’ chief complaints belong to one or multiple of the fol- in the media on personal appearance, these negative percep-
lowing categories: comfort, function, social, and appearance tions have only become more pronounced. Appropriate dental
[5]. prosthetics in terms of colour, shape and size are the most
Lack of comfort is generally the main source of urgency if common solution for patients who feel burdened aesthetically
a dental prosthetic is required. For example, a condition such by a lack of a complete dentition.
4958 j m a t e r r e s t e c h n o l . 2 0 1 9;8(5):4956–4964

tified at maximum values in excess of 1200 Newtons (N) in

2. Conventional prosthodontics extreme cases [16,17]. Fracture toughness is also a critical fac-
tor of clinical reliability, as it needs to be high enough to resist
2.1. Common materials for foundation components the rapid propagation of any flaws that may form [16]. For
dental applications, this property is commonly tested using
It is of paramount importance that these implants be not only the indentation fracture toughness technique (IF) [16]. Density
functional, but capable of enduring for their anticipated use- plays a key role is ensuring homogeneity in the material, and
ful life. In the case of fixed dental prosthetics (FDPs), namely it is a common goal of experimentation with ceramics manu-
crowns (single prosthetic), bridges (several joined prosthetics) facture to optimise this property. Higher densities correlate to
and dentures (full upper or lower jaw prosthetics), the aim is to lower porosity and thus higher hardness and fracture strength,
maximise this lifespan. This is desirable not only to avoid pre- both desirable characteristics of dental prosthetics. Hardness
mature failure of the implant, but also to avoid usually costly is commonly quantified via microhardness tests using instru-
and often impractical secondary removal surgery [2]. ments such as Knoop or Vickers diamond indenters [16].
In this field, the crown or bridge is referred to as the In line with the necessity for the patient to be satisfied
prosthesis and is supported by several foundation compo- with the appearance of the prosthetics, aesthetic properties,
nents used to fix it in place for long term functionality. In primarily colour and translucency, must be optimised. Cor-
the cases of fixed partial or complete dentures, the implant rectly matching the colours and contours of adjacent teeth
is considered to be the implant post that is screwed into the is often vital in maintaining patient satisfaction [5]. While
alveolar bone. This component houses an abutment, which is advancements in technology have increased the effectiveness
a threaded sleeve that allows for the attachment of the pros- of colour matching instruments such as spectrophotometers,
thesis itself (i.e. crown, bridge, denture etc.). The implant posts colorimeters and digital cameras, ultimately it is the material
are generally pure titanium (Grade 1–4) or a titanium alloy. The of the crown itself that will set the colour limitations [5,18].
system titanium-aluminium-vanadium, also known as Ti-6Al- Ceramics have a much more tooth-like natural colouration
4 V (Grade 23), is a commonly used alloy for this application compared to metals [19]. Translucency, which is a property
due to its higher hardness and better resistance to fatigue describing the level of light permitted and diffused through
when compared to commercially pure titanium [12,13]. the object, is emphasised as a primary factor for dictating
Whilst the implant post itself is usually titanium due to its aesthetic outcome [20]. This is mainly applicable to ceramic
superior machinability which is required for precision threads, restorations, considering metals are opaque. Correctly match-
the abutment material is selected with added aesthetic factors ing the translucency of the natural tooth structure is crucial,
in mind. Due to the translucency of some common mate- and is dependent on a variety of factors such as material
rials used to make dental crowns, ceramic abutments are and thickness, with thinner-walled crowns exhibiting higher
attracting increasing amounts of attention. This is not only translucency in general [5,20].
because of their similar colouration to that of a natural tooth, Whilst there are benchmark values for every mechanical
but also for their superior strength and fracture toughness and aesthetic parameter, it is inevitable that, over time in use,
when compared to metallic alternatives such as pure tita- these properties will degrade. This is known as hydrothermal
nium, and chrome-cobalt, dental gold and titanium alloys ageing or low temperature degradation (LTD) and is detri-
[14,15]. To bond the crown or bridge to the abutment(s), the mental to the application of the material [21,22]. LTD is not
most common technique is to use a luting agent known as a fully understood, though some believe it to be caused by the
dental cement. Ideally, the cement should be durable, provide humidity of the oral environment which can cause stress cor-
good adherence to natural and restorative materials, be non- rosion in certain materials [23]. Others hypothesize it to be
toxic, have adequate strength and low solubility [5]. Whilst no the result of residual stresses resulting from the presence of
variant exists that meets all the criteria, the most commonly water vapour [24]. Regarding metals such as titanium, LTD is
used cement is zinc phosphate. Its only limitation is in its not a significant issue due to the oxide film that forms on these
biocompatibility; however, these are well documented. Alter- prosthetics, making them highly resistant to corrosion in the
native cements include zinc polycarboxylate, glass ionomer oral environment [25]. In comparison, LTD is very common in
and resin-modified glass ionomer [5]. dental ceramics, and aging is considered a serious limitation
for these materials [21]. It must be noted that the ageing and
2.2. Mechanical, aesthetic and aging properties degradation of any prosthetic material can be accelerated by a
number of other factors, such as gingival conditions, implant
While the foundation components of the prosthetic are cru- geometries and loading cases, smoking and oral hygiene [25].
cial to ensure longevity and comfort, the crown forms the Therefore, with the intended long-term use of a fixed dental
outer layer of the structure. This not only means that it is the prosthetic, ageing properties play a large role in deeming a
most aesthetically influential component, but because of its material fit for application.
exposure to the external environment of the mouth, the con-
ditions it must endure are somewhat harsher than that of the 2.3. Common ceramics materials for dental prostheses
internal components. Regarding mechanical properties, flexu-
ral strength quantifies the ultimate stress required to fracture All-ceramic and metal-ceramic crowns are becoming a more
or plastically deform the specimen [16]. The prosthesis must attractive option for patients, especially for anterior tooth
exhibit good flexural strength to withstand the often eccentric restorations. This is mainly due to their good mimicking of
axial masticatory force on the tooth, which studies have quan- the optical and aesthetic properties of natural enamel and
 j m a t e r r e s t e c h n o l . 2 0 1 9;8(5):4956–4964 4959

dentine, with no sacrifices to biocompatibility or chemical alumina, corresponding to the maximum fracture toughness
durability [19,26]. Porcelain-fused-to-metal (PFM) restorations of approximately 7.45 MPa m1/2 and a Vickers hardness of
have been the most common metal-ceramic option for over 16.05 GPa. The increased fracture toughness relative to the
50 years [27]. Aesthetically, whilst porcelain is naturally solid individual monolithic materials was owed to the inhibition
white in colour, the fused metallic collar placed on the mar- of grain growth of the alumina by the addition of zirconia.
gins of the crown is often described as a “black line” by Aesthetically, ATZ performs very well as both zirconia and
patients with gingival recession [28,29]. This is often not deal alumina are naturally white, and the composite can be pro-
for those seeking a natural looking prosthetic. The translu- cessed to a good surface finish. However, the introduction of
cency of porcelain is also inconsistent, as it relies heavily on alumina reduces overall translucency, and this may not be
the scattering of light, which in turn is dependent on factors ideal in certain applications [38]. In terms of aging, the dop-
such as crystal content and particle size [28,30]. This makes for ing of alumina as low as 0.25 wt% to zirconia-based ceramics
complex manufacture to achieve satisfactory results. The frac- (yttrium partially stabilised) is known to improve the resis-
ture toughness of a PFM crown with 0.3 vol fraction of leucite tance of the material to LTD [38]. It does so by limiting the
is approximately 1.10 MPa m1/2 [31], which is satisfactory for amount of tetragonal grain growth during sintering, result-
most applications. The flexural strength varies depending on ing in a more stable structure [39]. Overall, ATZ exhibits the
the type of metal used as the substructure to strengthen highest flexural strength of any known ceramic, with values
it, as unreinforced feldspathic porcelain sees low values of ranging from 1800 to 2400 MPa at room temperature [38]. Due
55–65 MPa [32]. to its relatively good resistance to aging, high strength and aes-
Of the all-ceramic prosthetic materials, zirconium oxide thetic limitations, it shows the most promise for orthopaedic
(ZrO2 – zirconia) as a base material has shown great promise. implants or posterior FDPs.
This is not only due to its excellent mechanical properties, There are currently many options available for commer-
but also due to a unique phenomenon known as transforma- cially monolithic zirconium oxide materials. Not only is
tion toughening, first reported in 1975 [33]. This attribute sets the market size for dental implants growing annually and
it apart from other usually brittle ceramics in that, at room expected to continue increasing, but the proportion of these
temperature, pure zirconia exhibits a monoclinic (m) crystal implants made of monolithic zirconia is also forecast to grow.
structure, and when heated to 1170 ◦ C it transforms to a tetrag- This is evidenced in models analysing historical and forecast
onal (t) structure [34]. There is also a third cubic phase (f) that market growth for dental implants in the U.S, which project
occurs between 2370 ◦ C and melting point [34]. Upon cooling, the proportion of the total dental implant market made up
the t → m transformation induces an approximate 4.5% vol- by zirconia implants to almost double by 2024 [40]. It must
ume increase which could produce catastrophic failure, so it be noted that these models analyse the market trends for the
is typical to stabilize the zirconia with oxides such as mag- implants themselves, rather than the supported prosthetic,
nesia (MgO), yttria (Y2 O3 ), cerium oxide (CeO2 ) and calcium though are useful to highlight the increasing confidence in
oxide (CaO) [34,35]. This controls the stress, allows the more zirconia for dental applications due to advancing technology.
stable tetragonal structure to be present at room tempera- Monolithic zirconia variants are generally favourable over
ture, and also slows or halts crack propagation due to a t → m ATZ due to the lack of alumina present to lower the translu-
transformation local to the crack tip [34–36]. cency. Y-TZP is the most common of these, with the doping of
Yttria is the most established and well documented dopant yttria for the purpose of retaining a tetragonal crystal struc-
for inducing transformation toughening. Its addition in Yttria- ture, as has previously been explained. A common biomedical
stabilised tetragonal zirconia polycrystal (Y-TZP) decreases grade is 3 mol% yttria (3Y-TZP) [36]. This is readily available
the driving force of the t → m transformation and hence its as raw (green) powder, pre-sintered blanks that can be soft-
temperature [21]. This makes it possible for the metastable machined then sintered, or fully sintered blanks that require
tetragonal phase to be retained at room temperature, assum- hard-machining. Whilst it is a longer process, the pre-sintered
ing the yttria content is above 2 mol% [21]. The ZrO2 -Y2 O3 blanks are generally a more reliable option, as hard-machining
phase diagram shows the temperatures at which these phases of fully sintered blanks can cause a t → m transformation on
are present as yttria content is varied [21]. the surface, leading to microcracks and quicker LTD [41]. Cer-
In order to produce a composite that is wear resistant with amTec is a company that manufacture pre-sintered zirconia
higher fracture toughness and strength relative to its indi- blanks with diverse compositions and properties.
vidual monolithic forms, the zirconium oxide matrix can be CeramTec blanks are manufactured using a combination
toughened with alumina particles to form Alumina Tough- of uniaxial and hot isostatic pressing, and pressureless (con-
ened Zirconia (ATZ) [37]. Mechanical properties are dependent ventional) sintering, with sintering temperature specified to
not only on the ratio of alumina to zirconia, but also on the be 1450 ◦ C [42]. It is observed that the flexural strengths of
dopants used to stabilize each. This makes this composite all variants are substantially lower than those stated in lit-
quite versatile in terms of its applications. A study, performed erature for ATZ. This can partially be attributed to the low
in 2009, used Baikalox SM8 alumina and 3Y-TZP shows the proportions of alumina (Al2 O3 ). Flexural strength is seen to
change in hardness and fracture toughness as the propor- range from 840 to 1200 MPa and to grow with alumina content
tions are altered. The conditions under which these results whilst translucency diminishes. These values generally align
were obtained was uniaxial pressing under 50 MPa followed with those presented in literature, though some experiments
by 1500 ◦ C conventional sintering for 2 h [37]. report lower values due to influences of polishing and chosen
This study drew many notable conclusions about ATZ, shade of the ceramic [41,43]. Mechanical properties of 3Y-TZP
the optimal composition for dental application was 20 wt% are not only dependent on composition, but also on grain
4960 j m a t e r r e s t e c h n o l . 2 0 1 9;8(5):4956–4964

size which is dictated by sintering parameters (mainly, time for ceramic powder, particularly zirconia, are uniaxial com-
and temperature). As temperature and duration of sintering paction (dry pressing) and cold or hot isostatic compaction.
increases, so too does the grain size. Above a grain size of 1 ␮m, While the general cost to manufacture using each of these
3Y-TZP is more vulnerable to spontaneous t → m transforma- techniques can be commented on, it is important to note that
tion which can result in failure; below a grain size of 0.2 ␮m, cost is dependent on many factors beyond the technique itself.
the material loses its transformation toughening attribute and These include the level of expertise available at the place of
fracture toughness therefore diminishes [38]. In line with this, manufacture, the level of detail required for the product, and
another study concluded that the critical grain size to retain the machinery/tooling brands available to the technician. For
the t phase is between 0.2 ␮m and 0.6 ␮m, depending on yttria example, it is generally accepted that hot isostatic pressing is
content [44]. A study, performed in 2007, using a specimen the most expensive technique to manufacture zirconia prod-
of similar composition to those offered by CeramTec showed ucts, due to increased cycle times and higher running costs.
the variation of fracture strength, a good indicator of fracture However, depending on the degree to which the manufacturer
toughness, with grain size. This study concluded that a grain has refined the cycle parameters, cycle times for this tech-
size of 380 nm (0.38 ␮m) maximizes fracture strength [45]. nique may be reduced sufficiently to offset these additional
Just as in ATZ, the CeramTec products are purposefully costs and make it more cost-effective relative to the alterna-
doped with trace amounts of alumina to decelerate LTD. It tives. Such refinements are currently being explored to make
is important to note that increased amounts of alumina do these higher-quality products more accessible to the average
not necessarily correlate to higher resistance to LTD; rather consumer.
the optimal doping proportion for 3Y-TZP is widely agreed
to be 0.25 wt% [46]. This again varies according to sintering 3.1. Dry pressing
conditions. It gives merit to the notion that the monolithic zir-
conia form, whilst inferior in terms of flexural strength, is not Dry pressing is a process of uniaxial compaction of the ceramic
severely disadvantaged in terms of its resistance to hydrother- powder via means of hydraulically operated upper and (occa-
mal degradation in comparison to its composite form. A 2015 sionally) lower punches. In dental ceramics, this technology
study confirmed this for sintering temperatures of 1450 ◦ C and is beginning to age with access to isostatic pressing becoming
1550 ◦ C, with both experiments confirming that the Zpex 3Y- easier. In green state zirconia (i.e. raw, non-sintered zirconia
TZP specimen (300 MPa cold isostatic pressed) with 0.25 wt% powder), this method is known to create density hetero-
alumina took longer to degrade than with 5 wt% alumina [47]. geneities which makes for inconsistent mechanical properties
This was based on vol% of unstable monoclinic phase in the throughout the blank [51]. This makes dry pressing unsuitable
specimen after 40 h of simulated hydrothermal treatment. for larger pieces such as bridges, where the density irregulari-
It should be noted that experiments have been performed ties will be more pronounced; however, it is still often viable for
to assess the feasibility of TZP specimens with higher yttria single crowns [51]. The Weibull modulus is a widely accepted
content (e.g. 4Y-TZP). These experiments concluded that 4Y parameter to describe the structural reliability of brittle dental
samples had a higher resistance to hydrothermal ageing when ceramics such as zirconia [52]. It takes into account a variety
compared to lower yttria content, quantifiable by the lower of factors, such as the probability of failure and the fracture
fraction of unstable monoclinic phase over time [48]. Whilst strength [53]. Lower Weibull modulus correspond to a more
this is ideal, the advantages are negated by the increase in frequent presence of microstructural flaws and defects, which
average grain size [48] and substantial decrease in fracture lead to a lower reliability [52]. The Weibull modulus for uni-
toughness [47] as yttria content is increased. For this reason, axially pressed 3Y-TZP blanks, based on limited literature, is
3 mol% yttria is widely considered to be the optimal dopant usually approximately 5 (using a 3-point flexural test), and
content to balance aging and mechanical properties. is therefore is low relative to other methods [54]. The main
advantage of dry pressing is the comparatively low equip-
ment and running costs. Also, in many cases it can produce
3. Manufacturing technologies for more precise shapes resulting in less required post milling
all-ceramic dental implants and therefore less wastage of material [51]. For this reason,
it is common to use dry pressing as a pre-processing phase
Before the sintering process can take place, a procedure of to obtain shape, before isostatic pressing ensures homogene-
forming and shaping must be undertaken for ceramics. This is ity. Due to the decreased use of this shaping method, there is
achieved using a combination of moulding, compaction and in not a wide range of previous studies to validate conventional
some cases heat to produce a ceramic body with the desired parameters; however, the few that are available confirm a rec-
shape and size. The aim is to increase the solid content in ommended uniaxial compaction pressure of 150–200 MPa for
the material to the highest possible level during compaction, 3Y-TZP powder [46,49].
which means minimising or at least regulating pore size and
frequency [49]. Pores, which are voids in the microstructure of 3.2. Cold isostatic pressing
the material, have been experimented with using zirconia, and
the results showed a decrease in both elastic modulus (stiff- Cold Isostatic Pressing (CIP) makes use of a high-pressure
ness) and hardness of the material as pore content increased fluid chamber to compact ceramic powder that is contained
[50]. It is therefore not ideal for dental ceramics, which require inside a flexible mold. Isostatic pressing in general is much
intermediate hardness and high stiffness as evidenced, to more comprehensive in terms of ensuring high and homoge-
have a high porosity. Three traditionally used techniques neous density (i.e. less porosity) throughout the zirconia blank
 j m a t e r r e s t e c h n o l . 2 0 1 9;8(5):4956–4964 4961

[51,53,55]. This high uniformity yields mechanically stronger when considering the surface damage imparted on the sam-
blanks when compared to uniaxial pressing, and makes for ple by the milling procedure. Currently the only disadvantages
an easier and more effective sintering process [55]. Literature come in the financial viability of these systems, with the initial
shows that the mean Weibull modulus for CIP blanks with investment being quite high [60].
composition and characteristics alike CeramTec blanks ranges An important characteristic of a successful dental restora-
from 6 to 8 based on a 3-point flexural test [53,54]. However, tion is marginal adaptation. This essentially describes the
the shapes produced are often not as precise, and the extra degree to which the prosthesis matches the surrounding
milling required to refine the product to a satisfactory level teeth dimensionally. Inadequate marginal adaptation leads to
causes uneconomical material wastage [51]. Compaction pres- plaque accumulation, which in turn can cause microleakage
sure for CIP is cited in literature as 300 MPa, though this can (i.e. infiltration of bacteria), as well as endodontic inflam-
be altered to as high as 1000 MPa if required [56,57]. mation and periodontal diseases [62]. CAD/CAM technology,
which is reliant on dimensional predictions that account for
3.3. Hot isostatic pressing shrinkage during sintering, has demonstrated an improve-
ment in marginal adaptation of dental zirconia prosthetics
The concept of Hot Isostatic Pressing (HIP) is similar to that [63,64]. Some CAM systems can produce a marginal discrep-
of CIP, though it makes use of pressurised and heated inert ancy as low as 9 ␮m (prior to cementation) [63], which is
gases such as argon rather than room temperature fluid. This well below the widely accepted limit of 120 ␮m [62]. This is
is often not only a forming process, but a finishing process as additional evidence to suggest that the use of CAD/CAM will
well, since the result can be a fully sintered product. The pro- further streamline the dental ceramic fabrication process and
cess takes place in a furnace, with the container to shape the provide more reliability for the patient.
powder being made of a high-melting point sheet metal. HIP is
advantageous in that it produces the highest density products
with isotropic (direction-independent) properties; however, its 4. Sintering of zirconia dental prosthetics
main disadvantage comes in the high costs associated with
both the initial investment and the general running costs due As has been evidenced, characteristics such as flexural
to heating. To compound this, products of HIP are much harder strength and resistance to LTD are largely dependent on grain
relative to CIP and dry pressing, meaning the final shape size for polycrystalline materials such as zirconia. The sin-
can only be refined using heavy milling techniques, further tering process has a direct influence on the resultant grain
increasing overall cost. In terms of the mechanical properties growth rate, which, if too high, will begin to adversely affect
achievable using HIP, virtually fully dense 3Y-TZP blanks have flexural strength and will make it difficult to obtain high den-
been obtained, having a porosity of less than 0.15%. Mechan- sity [45,65]. Crystalline content in ceramics is also known to
ical properties are seen to vary vastly with temperature for dictate translucency [66], and a study performed in 2013 using
HIP [58]. Fracture toughness values as high as 1600 MPa, and various 3Y-TZP blanks concluded that high translucency in the
Weibull modulus in excess of 10.6 (based on 3-point flexu- products corresponded to smaller grain sizes and shorter sin-
ral test) have been achieved for fully dense blanks [58]. Fully tering times [67]. As such, conventional sintering techniques
dense HIPed blanks can have grain sizes of 0.36 ␮m or less and are being challenged by new innovations that aim to optimise
can resist LTD in harsh hydrothermal environments, though key parameters such as temperature, heat rate, and sintering
the more typical results (94.5% density, 0.6 ␮m or less grain (dwelling) time.
size) resisted aging in air for 2000 h [58]. Conventionally, HIP
temperature and pressure ranges from 1300 ◦ C–1600 ◦ C and 4.1. Conventional sintering
140 MPa–150 MPa respectively, and the process duration is usu-
ally 1 h [58,59]. The conventional sintering process consists of heating a pre-
compacted blank in a high-temperature furnace to densify
3.4. CAD/CAM technology the product. The pivotal parameters with this technique are
dwelling time, maximum furnace temperature and heat rate
Evidence from both materials development and long-term supplied to reach the maximum temperature. A study per-
clinical studies strongly suggest promise for the field formed in 2013 used conventional sintering to evaluate the
of CAD/CAM (Computer-Aided Design/Manufacturing) as a effect of sintering temperature on flexural strength and grain
future trend in dental ceramics. This subtractive manufac- size. It used Ceramill ZI Y-TZP blanks, maximum sintering
turing technology allows the technician to prepare the tooth temperatures ranging from 1300 ◦ C to 1700 ◦ C, a heat rate of
restoration model in software, and relay the information to 8 ◦ C/min and a duration of 120 min. It ultimately concluded
a computer assisted processing machine for milling from a that conventional sintering was optimal in terms of flexural
blank [60]. The CAD/CAM methodology has many advantages strength (1100 MPa–1250 MPa) for sintering temperatures rang-
in comparison to traditional physical impression-making. ing from 1400 ◦ C to 1550 ◦ C [66]. Another study conducted in
Time to fabricate is much lower and less prone to human 2008 used conventional sintering between 1100 ◦ C and 1500 ◦ C
error [60]. Measurements and fabrication are also very pre- for Zpex 3Y-TZP for a duration of 1 min at a heat rate of
cise and thus final quality is high [60]. In fact, CAM zirconia 5 ◦ C/min. This was to measure the relation between density
with no other surface treatment (i.e. polishing, sandblasting and grain size. It concluded that the optimal grain size to
etc.) has been experimented with to have a characteristic flex- give the highest density (98.8%) was 275 nm [68]. It also found
ure strength of approximately 821 MPa [61]. This is promising that as temperature was increased, whilst densification was
4962 j m a t e r r e s t e c h n o l . 2 0 1 9;8(5):4956–4964

marginal, grain growth rate was high which makes controlling prosthodontic industry if new and alternative sintering tech-
the process difficult [68]. niques, such as two-step sintering, were investigated for their
These results are confirmed by another investigation into blanks. Experimentation with two-step sintering has shown
conventional sintering conducted in 2012, also using Zpex positive results in improving mechanical properties. There are
blanks. It found an average grain size of approximately 256 nm also no significant cost increases associated with this method
with 98.3% density at a sintering temperature of 1400 ◦ C [69]; compared to conventional sintering, as similar equipment
though the dwelling time was much longer at 60 min mak- is utilised for both. The objective of further investigations
ing for a more uniform material. From the literature available, would be to optimise key parameters such as hardness, flex-
it is apparent that conventional sintering can achieve grain ural strength, and grain growth and size, whilst maintaining
sizes that produce desirable mechanical and optical proper- the superior aesthetic properties they possess. These can be
ties. However, the high temperatures required lead to fast compared to the results of the prescribed sintering conditions,
grain growth which could damage quality consistency. and to products fully processed from green zirconia powder.

4.2. Two-step sintering

Conflicts of interest
Initially developed in the 1990’s by Chu et al. [70], with
The authors declare no conflicts of interest.
subsequent refinements by Chen and Wang [71], the two-
step sintering process (TSS-CW) has become widely used. It
consists of high temperature heating to T1 ◦ C followed by sus- references
tained structural freezing to T2 ◦ C, and was claimed to achieve
densification with no grain growth within a certain tempera-
ture range [72]. In 2008, the TSS-CW method was used with [1] Khan W, Muntimadugu E, Jaffe M, Domb AJ. Implantable
Zpex 3Y-TZP, being heated to T1 (1250 ◦ C–1350 ◦ C) at 5 ◦ C/min, medical devices. In: Focal controlled drug delivery. Springer;
held for 1 min, then cooled to T2 (1050 ◦ C–1250 ◦ C) and held 2014. p. 33–59.
between 2 h and 30 h [68]. When compared to conventional [2] Jiang G, Zhou DD. Technology advances and challenges in
sintering under similar conditions, this method showed a hermetic packaging for implantable medical devices. In:
Implantable neural prostheses 2. Springer; 2009. p. 27–61.
slower grain growth rate [68]. It also produced a higher densi-
[3] Joung Y-H. Development of implantable medical devices:
fication at a smaller grain size (110 nm compared to 275 nm), from an engineering perspective. Int Neurourol J
with optimal conditions being the 1300 ◦ C-1050 ◦ C, 30 h cycle 2013;17(3):98–106.
[68]. [4] Australian regulatory guidelines for medical devices
A study performed in 2004 also investigated the TSS-CW (ARGMD); 2010.
method on 3Y-TZP. It used a heat rate of 10 ◦ C/min to reach [5] Rosenstiel SF, Land MF. Contemporary fixed prosthodontics.
Elsevier Health Sciences; 2015.
a T1 of 1500 ◦ C, was held for 5 min, then cooled to a T2 of
[6] Cope G, Cope A. Gingivitis: symptoms, causes and treatment.
1300 ◦ C and held for 10 h [73]. It resulted in a flexural strength
Dent Nurs 2011;7(8):436–9.
of 1078 MPa compared to the 295 MPa achieved using conven- [7] Petersen PE, Bourgeois D, Ogawa H, Estupinan-Day S, Ndiaye
tional sintering [73]. Grain size at optimal density was also C. The global burden of oral diseases and risks to oral health.
smaller using TSS-CW (560 nm compared to 1050 nm) [73]. The Bull World Health Org 2005;83:661–9.
differences in the resulting grain sizes for the studies can be [8] Abd-Elmeguid A, Yu DC. Dental pulp neurophysiology: part
attributed to differing forming methods (pressing vs. injec- 1. Clinical and diagnostic implications. J Can Dent Assoc
2009;75(1).
tion moulding) and powder particle sizes (75 nm vs. 270 nm)
[9] Turgut MD, Genç GA, Başar F, Tekçiçek MU. The effect of early
[68,72,73]. Nevertheless, both studies show vast improvement loss of anterior primary tooth on speech production in
in grain growth rate and grain size achieved using the TSS- preschool children. Turk J Med Sci 2012;42(5):867–75.
CW method, which will produce preferable mechanical and [10] Rosenberg M. Bad breath and periodontal disease: how
optical properties for the dental prosthetics. related are they? J Clin Periodontol 2006;33(1):29–30.
[11] Oosterhaven SP, Westert GP, Schaub RM. Perception and
significance of dental appearance: the case of missing teeth.
5. Conclusions Community Dent Oral Epidemiol 1989;17(3):123–6.
[12] Jorge JRP, Barão VA, Delben JA, Faverani LP, Queiroz TP,
Assunçao WG. Titanium in dentistry: historical
The use of zirconia in dental ceramics is evidently becoming
development, state of the art and future perspectives. J
quite established, with major advancements in the last decade Indian Prosthodont Soc 2013;13(2):71–7.
especially on 3Y-TZP. This can be attributed to its capabili- [13] Niinomi M. Mechanical biocompatibilities of titanium alloys
ties of meeting all key patient satisfaction criteria (comfort, for biomedical applications. J Mech Behav Biomed Mater
functionality, social aspects, appearance). 3Y-TZP prosthetics 2008;1(1):30–42, 2008/01/01/.
are commonly formed and machined from partially sintered ˛
[14] Ziebowicz ˛
B, Ziebowicz ˛
A, Baczkowski B, Kajzer W, Kajzer A.
Biomechanical analysis of individual all-ceramic abutments
blanks, such as those produced by CeramTec, due to increased
used in dental implantology. Arch Metall Mater
reliability and less intense machining demands. While there 2016;61(3):1357–62.
has been extensive research and experimentation on the opti- [15] Rutkunas V, Bukelskiene V, Sabaliauskas V, Balciunas E,
misation of key processes such as pressing and sintering, there Malinauskas M, Baltriukiene D. Assessment of human
was inevitably going to be knowledge gaps for such a newly gingival fibroblast interaction with dental implant abutment
realised technology. It will be beneficial to CeramTec and to the materials. J Mater Sci Mater Med 2015;26(4):169. March 25.
 j m a t e r r e s t e c h n o l . 2 0 1 9;8(5):4956–4964 4963

[16] Yilmaz H, Aydin C, Gul BE. Flexural strength and fracture [39] Silva NR, et al. Performance of zirconia for dental healthcare.
toughness of dental core ceramics. J Prosthet Dent Materials 2010;3(2):863–96.
2007;98(2):120–8, 2007/08/01/. [40] Grand View Research, D̈ental Implants Market Size, Share &
[17] Flanagan D. Bite force and dental implant treatment: a short Trends Analysis Report By Product (Titanium Implants,
review. Med Devices (Auckl) 2017;10:141. Zirconium Implants), By Region (North America, Europe, Asia
[18] Chu SJ, Trushkowsky RD, Paravina RD. Dental color matching Pacific, Latin America, MEA), And Segment Forecasts, 2018 -
instruments and systems. Review of clinical and research 2024; GVR-1-68038-566-3,M̈arket Research Report 2018.
aspects. J Dent 2010;38:e2–16. [41] Denti L. Comparative study of three yttria-stabilized zirconia
[19] Özkurt Z, Kazazoğlu E. Zirconia dental implants: a literature formulations in colored vs natural shades. Int J Appl Eng Res
review. J Oral Implantol 2011;37(3):367–76. Dev 2017;12(8):1452–9.
[20] Wang F, Takahashi H, Iwasaki N. Translucency of dental [42] CeramTec. (10.01.2019), Available:
ceramics with different thicknesses. J Prosthet Dent [Link] dental ceramics blanks
2013;110(1):14–20, 2013/07/01/. [Link].
[21] Chevalier J, Gremillard L, Deville S. Low-temperature [43] Cavalcanti AN, Foxton RM, Watson TF, Oliveira MT, Giannini
degradation of zirconia and implications for biomedical M, Marchi GM. Y-TZP ceramics: key concepts for clinical
implants. Annu Rev Mater Res 2007;37:1–32. application. Oper Dent 2009;34(3):344–51.
[22] Wu ZK, Li N, Yan JZ, Zhao WQ. Effect of hydrothermal aging [44] Watanabe W, Iiu S, Fukuura I. Aging behavior of Y-TZP. In:
on the phase stability, microstructure and mechanical Science and technology of zirconia II; 1983.
properties of dental 3Y-TZP ceramics. Appl Mech Mater [45] Eichler J, Rödel J, Eisele U, Hoffman M. Effect of grain size on
2014;529:251–5. Trans Tech Publ. mechanical properties of submicrometer 3Y-TZP: fracture
[23] Papanagiotou HP, Morgano SM, Giordano RA, Pober R. In vitro strength and hydrothermal degradation. J Am Ceram Soc
evaluation of low-temperature aging effects and finishing 2007;90(9):2830–6.
procedures on the flexural strength and structural stability [46] Kosmač T, Kocjan A. Ageing of dental zirconia ceramics. J Eur
of Y-TZP dental ceramics. J Prosthet Dent 2006;96(3):154–64. Ceram Soc 2012;32(11):2613–22, 2012/08/01/.
[24] Sato T, Shimada M. Transformation of yttria-doped [47] Zhang F, et al. Critical influence of alumina content on the
tetragonal ZrO2 polycrystals by annealing in water. J Am low temperature degradation of 2–3 mol% yttria-stabilized
Ceram Soc 1985;68(6), 356-356. TZP for dental restorations. J Eur Ceram Soc
[25] Revathi A, Borrás AD, Muñoz AI, Richard C, Manivasagam G. 2015;35(2):741–50.
Degradation mechanisms and future challenges of titanium [48] Yamashita I, Tsukuma K, Tojo T, Kawaji H, Atake T.
and its alloys for dental implant applications in oral Synchrotron X-Ray study of the crystal structure and
environment. Mater Sci Eng C 2017;76:1354–68. hydrothermal degradation of yttria-stabilized tetragonal
[26] Kelly JR, Benetti P. Ceramic materials in dentistry: historical zirconia polycrystal. J Am Ceram Soc 2008;91(5):1634–9.
evolution and current practice. Aust Dent J 2011;56:84–96. [49] Sun J, Gao L. Influence of forming methods on the
[27] Christensen GJ. Porcelain-fused-to-Metal versus microstructure of 3Y-TZP specimens. Ceram Int
zirconia-based ceramic restorations, 2009. J Am Dent Assoc 2003;29(8):971–4, 2003/01/01/.
2009;140(8):1036–9, 2009/08/01/. [50] Li J, Wang X, Lin Y, Deng X, Li M, Nan C. In vitro cell
[28] Vichi A, Louca C, Corciolani G, Ferrari M. Color related to proliferation and mechanical behaviors observed in porous
ceramic and zirconia restorations: a review. Dent Mater zirconia ceramics. Materials 2016;9(4):218.
2011;27(1):97–108, 2011/01/01/. [51] G. Arnaud, The truth about zirconia, Dent Tech, 80, 81, 59–72.
[29] Newsome P, Owen S. Improving your margins. Int Dent SA Available online:
2009;11:36–42. [Link]
[30] Brodbelt R, O’brien W, Fan P. Translucency of dental 8058466/[Link]
porcelains. J Dent Res 1980;59(1):70–5. (accessed on 30 November 2018).
[31] Quinn JB, Quinn GD, Sundar V. Fracture toughness of [52] Stawarczyk B, Özcan M, Trottmann A, Hämmerle CH, Roos
veneering ceramics for fused to metal (PFM) and zirconia M. Evaluation of flexural strength of hipped and presintered
dental restorative materials. J Res Natl Inst Stand Technol zirconia using different estimation methods of Weibull
2010;115(5):343. statistics. J Mech Behav Biomed Mater 2012;10:227–34.
[32] Seghi R, Daher T, Caputo A. Relative flexural strength of [53] Siarampi E, Kontonasaki E, Papadopoulou L, Kantiranis N,
dental restorative ceramics. Dent Mater 1990;6(3):181–4. Zorba T, Paraskevopoulos KM, Koidis P. Flexural strength and
[33] Garvie R, Hannink R, Pascoe R. Ceramic steel? Nature the probability of failure of cold isostatic pressed zirconia
1975;258(5537):03. core ceramics. J Prosthet Dent 2012;108(2):84–95.
[34] Al-Amleh B, Lyons K, Swain M. Clinical trials in zirconia: a [54] Xu Y, Han J, Lin H, An L. Comparative study of flexural
systematic review. J Oral Rehabil 2010;37(8):641–52. strength test methods on CAD/CAM Y-TZP dental ceramics.
[35] Daguano J, Santos C, Souza R, Balestra R, Strecker K, Elias C. Regen Biomater 2015;2(4):239–44, 10/14.
Properties of ZrO2–Al2O3 composite as a function of [55] Lyubushkin R, Sirota V, Ivanov O. Fabrication and properties
isothermal holding time. Int J Refract Metals Hard Mater of zirconium ceramic from zirconium dioxide nanopowder.
2007;25(5-6):374–9. Glass Ceram 2011;68(1-2):61–4.
[36] Denry I, Kelly JR. State of the art of zirconia for dental [56] Maca K, Trunec M, Dobsak P. Bulk zirconia nanoceramics
applications. Dent Mater 2008;24(3):299–307. prepared by cold isostatic pressing and pressureless
[37] Nevarez-Rascon A, Aguilar-Elguezabal A, Orrantia E, sintering. Rev Adv Mater Sci 2005;10(1):84–8.
Bocanegra-Bernal M. On the wide range of mechanical [57] Trunec M, Maca K. Compaction and pressureless sintering of
properties of ZTA and ATZ based dental ceramic composites zirconia nanoparticles. J Am Ceram Soc 2007;90(9):2735–40.
by varying the Al2O3 and ZrO2 content. Int J Refract Metals [58] Muñoz-Saldaña J, Balmori-Ramírez H, Jaramillo-Vigueras D,
Hard Mater 2009;27(6):962–70. Iga T, Schneider G. Mechanical properties and
[38] Osman R, Swain M. A critical review of dental implant low-temperature aging of tetragonal zirconia polycrystals
materials with an emphasis on titanium versus zirconia. processed by hot isostatic pressing. J Mater Res
Materials 2015;8(3):932–58. 2003;18(10):2415–26.
4964 j m a t e r r e s t e c h n o l . 2 0 1 9;8(5):4956–4964

[59] Iijima T, Homma S, Sekine H, Sasaki H, Yajima Y, Yoshinari [67] Kim M-J, Ahn J-S, Kim J-H, Kim H-Y, Kim W-C. Effects of the
M. Influence of surface treatment of yttria-stabilized sintering conditions of dental zirconia ceramics on the grain
tetragonal zirconia polycrystal with hot isostatic pressing on size and translucency. J Adv Prosthodont 2013;5(2):161–6,
cyclic fatigue strength. Dent Mater J 2013;32(2):274–80. 05/30.
[60] Davidowitz G, Kotick PG. The use of CAD/CAM in dentistry. [68] Mazaheri M, Simchi A, Golestani-Fard F. Densification and
Dent Clin 2011;55(3):559–70. grain growth of nanocrystalline 3Y-TZP during two-step
[61] Wang H, Aboushelib MN, Feilzer AJ. Strength influencing sintering. J Eur Ceram Soc 2008;28(15):2933–9.
variables on CAD/CAM zirconia frameworks. Dent Mater [69] Borrell A, Salvador MD, Rayón E, Peñaranda-Foix FL.
2008;24(5):633–8. Improvement of microstructural properties of 3Y-TZP
[62] Contrepois M, Soenen A, Bartala M, Laviole O. Marginal materials by conventional and non-conventional sintering
adaptation of ceramic crowns: a systematic review. J Prosthet techniques. Ceram Int 2012;38(1):39–43, 2012/01/01/.
Dent 2013;110(6):447–54, e10, 2013/12/01/. [70] Chu MY, De Jonghe LC, Lin MK, Lin FJ. Precoarsening to
[63] Gonzalo E, Suárez MJ, Serrano B, Lozano JF. A comparison of improve microstructure and sintering of powder compacts. J
the marginal vertical discrepancies of zirconium and metal Am Ceram Soc 1991;74(11):2902–11.
ceramic posterior fixed dental prostheses before and after [71] Chen I-W, Wang X-H. Sintering dense nanocrystalline
cementation. J Prosthet Dent 2009;102(6):378–84. ceramics without final-stage grain growth. Nature
[64] Goldin EB, Boyd NW III, Goldstein GR, Hittelman EL, 2000;404(6774):168.
Thompson VP. Marginal fit of leucite-glass pressable ceramic [72] Lóh N, Simão L, Faller C, De Noni A Jr, Montedo O. A review of
restorations and ceramic-pressed-to-metal restorations. J two-step sintering for ceramics. Ceram Int
Prosthet Dent 2005;93(2):143–7. 2016;42(11):12556–72.
[65] Anselmi-Tamburini U, Garay J, Munir ZA. Fast [73] Lee S-Y. Sintering behavior and mechanical properties of
low-temperature consolidation of bulk nanometric ceramic injection-molded zirconia powder. Ceram Int
materials. Scr Mater 2006;54(5):823–8. 2004;30(4):579–84, 2004/01/01/.
[66] Stawarczyk B, Özcan M, Hallmann L, Ender A, Mehl A,
Hämmerlet CH. The effect of zirconia sintering temperature
on flexural strength, grain size, and contrast ratio. Clin Oral
Investig 2013;17(1):269–74.