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Metallurgical and interfacial characterization of PFM CoCr dental alloys fabricated via
casting, milling or selective laser melting. Dent Mater (2014), http://dx.doi.org/10.1016/j.dental.2014.01.008
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Metallurgical and interfacial characterization of
PFM CoCr dental alloys fabricated via casting,
milling or selective laser melting
Y.S. Al Jabbari
a,b,
, T. Koutsoukis
a
, X. Barmpagadaki
c
, S. Zinelis
d,a
a
Dental Biomaterials Research and Development Chair, College of Dentistry, King Saud University, P.O. Box 60169,
Riyadh 11545, Saudi Arabia
b
Department of Prosthetic Dental Sciences, College of Dentistry, King Saud University, P.O. Box 60169, Riyadh
11545, Saudi Arabia
c
Private Practice, Githiou 81 Str, Pireas 18544, Greece
d
Department of Biomaterials, School of Dentistry, University of Athens, 2 Thivon Str, Goudi 11527, Athens, Greece
a r t i c l e i n f o
Article history:
Received 29 April 2013
Received in revised form
25 September 2013
Accepted 16 January 2014
Available online xxx
Keywords:
SLM
Fabrication techniques
CoCr dental alloy
Metalceramic interface
a b s t r a c t
Objectives. Bulk and interfacial characterization of porcelain fused to metal (PFM) CoCr
dental alloys fabricated via conventional casting, milling and selective laser melting.
Methods. Three groups of metallic specimens made of PFMCoCr dental alloys were prepared
using casting (CST), milling (MIL) and selective laser sintering (SLM). The porosity of the
groups was evaluated using X-ray scans. The microstructures of the specimens were evalu-
ated via SEM examination, EDX and XRD analysis. Vickers hardness testing was utilized to
measure the hardness of the specimens. Interfacial characterization was conducted on the
porcelain-covered specimens from each group to test the elemental distribution with and
without the application of INmetalbond. The elemental distribution of the probed elements
was assessed using EDX line prole analysis. Hardness results were statistically analyzed
using one-way ANOVA and HolmSidaks method (=0.05).
Results. X-ray radiography revealed the presence of porosity only in the CST group. Different
microstructures were identied among the groups. Together with the phase matrix, a sec-
ond phase, believed to be the Co
3
Mo phase, was also observed by SEMand subsequent XRD
analysis. Cr
7
C
3
and Cr
23
C
6
carbides were also identied via XRD analysis in the CST and MIL
groups. The hardness values were 32012HV, 2975HV and 37110HV, and statistically
signicant differences were evident among the groups.
Signicance. The microstructure and hardness of PFM CoCr dental alloys are dependent
on the manufacturing technique employed. Given the differences in microstructural and
hardness properties among the tested groups, further differences in their clinical behavior
are anticipated.
2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
Corresponding author at: Dental Biomaterials Research and Development Research Chair, College of Dentistry, King Saud University, P.O.
Box 60169, Riyadh 11545, Saudi Arabia. Tel.: +966 1 4698312; fax: +966 1 4698313.
E-mail addresses: yaljabbari@ksu.edu.sa, youssef14@hotmail.com(Y.S. Al Jabbari).
0109-5641/$ see front matter 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.dental.2014.01.008
Please cite this article in press as: Al Jabbari YS, et al. Metallurgical and interfacial characterization of PFM CoCr dental alloys fabricated via
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1. Introduction
Technological developments have led to the implementa-
tion of novel manufacturing processes in everyday dental
practice. In recent decades, digitalized technologies have been
employed for the production of metallic structures, mainly in
prosthetic dentistry [15]. These technologies can be classied
as based on subtractive manufacturing, such as the milling
of pre-manufactured materials assisted by computer-aided
design/computer-aided manufacturing (CAD/CAM) systems
[1,2,57], or on additive manufacturing, such as the recently
developed selective laser melting (SLM) technique [3,4,810].
Although CAD/CAM has long been directly associated with
the milling procedure in dental literature, it should be
mentioned that SLM is also classied as CAD/CAM technol-
ogy.
As a recently introduced technique, SLM has attracted
the worldwide interest of research groups for the manufac-
turing of dental metallic structures. In prosthetic dentistry,
most studies on SLM have focused on CoCr dental alloys
[3,8,9,1120]; signicantly fewer studies have been per-
formed on Ti alloys [4,21] or the costly precious alloys
[3,12]. These studies have primarily focused on the evalua-
tion of the marginal and/or internal t of the restorations
[3,6,9,13,1517,20], whereas other studies have tested the
bond strength with dental porcelain [8,18,21], internal poros-
ity [4], effect of surface treatments on microroughness [14]
and electrochemical properties [19]. However, the compara-
tive analyses of specic properties among metallic structures
made using SLM and conventional techniques are limited
[13,21]; thus, the effect of the SLM technique on mechani-
cal, electrochemical, microstructural and other properties is
still unknown. Given the large differences in the manufac-
turing process between casting, which uses the complete
melting and overheating of casting materials, the milling of
a prefabricated metal block and SLM of a ne metallic pow-
der, large differences in microstructural characteristics are
anticipated. These microstructural differences may also dif-
ferentiate the interfacial characterizationof metallic elements
at the metalporcelain interface. Although common for other
prosthetic dental alloys, interfacial analyses of CoCr alloys
cast or milled with porcelain are still absent from the dental
literature. Therefore, the aim of this study was to metal-
lurgically and interfacially characterize CoCr dental alloys
prepared by casting, milling and SLM techniques. The null
hypothesis was that there would be signicant dissimilari-
ties among the groups prepared by different manufacturing
techniques.
2. Materials and methods
2.1. Specimen preparation
Three groups (CST, MIL, and SLM) were prepared using CoCr
dental alloys as indicated by the manufacturers. The spec-
imens of the CST group were fabricated by the traditional
casting technique using CoCr raw material; those of the MIL
group were milled off a prefabricated block and the specimens
of the SLMgroup were fabricated by the SLMtechnique using
CoCr mixed powder. The brand names, manufacturers and
elemental composition of the alloys tested are presented in
Table 1.
In the CST group, 12 wax patterns (IQ sticks, Yeti Den-
tal, Engen, Germany) were invested with phosphate-bonded
investment (GC Stellavest, GC Europe NV, Belgium) with
dimensions of 0.5mm3mm25mm. The mold was pre-
heated at 910
C and cast with VI-COMP alloy at 1450
C using
a centrifugal casting machine (Ducatron S3, UginDentaire,
Seyssins, France). The moldwas left to cool down to roomtem-
perature and the specimens were then divested and cleaned
by sandblasting with alumina particles (100m).
A prefabricated block of a commercial CoCr dental
alloy (Okta-C) was milled to fabricate a dental restoration
using the Organical Multi Milling/Grinding CAD/CAM system
(R+K CAD/CAM Technologie, Berlin, Germany). A rectangular-
shaped wax pattern was digitized and the specimens were
cut to their nal dimensions (0.5mm3mm25mm) using
the Organical Multi Milling/grinding machine (R+K CAD/CAM
Technologie).
The laser-sinteredspecimens were preparedfromcommer-
cial CoCr powder (ST2725G) using a dental laser sintering
device (PM 100 Dental System, Phenix Systems, Clermont-
Ferrard, France) equipped with a 500W Yb-ber laser, at a
temperature of 1650
C; the laser systemhadthe ability toweld

across a controlled (XY)-axis coordinate systemwith a Z-axis
tolerance of 0.0254mm. The CoCr powder was applied to a
stainless steel plate and was laser-sintered upwards in subse-
quent layers after a 20-m-thick layer was completed until the
nal product was generated. Following laser sintering, the sin-
tered parts were cooled down to furnace temperature. In total,
12 specimens with dimensions of 0.5mm3mm25mm
were fabricated using this technique.
2.2. X-ray testing
All specimens of all groups were then examined for internal
porosity using a dental X-ray unit (Orix 70, Ardet, Milan, Italy)
operating at 70kV and 5mA with an exposure time of 15s.
Digital images were collected from all specimens, and the X-
ray images were assessed by the naked eye.
2.3. SEM-EDX characterization
For microstructural characterization, three specimens of each
group were examined using a SEM (JSM 6610 LV, Jeol Ltd.,
Tokyo, Japan) equipped with an X-ray EDS microanalysis (EDX)
unit (Oxford Instruments, Abingdon, UK). All examined sur-
faces were ground using SiC paper (2202000 grit) under
continuous water cooling and polished in a grinding polishing
machine (Ecomet III, Bueler, Lake Bluff, IL, USA) using a dia-
mond paste (DP Paste, Struers, Copenhagen, Denmark). The
specimens were then cleaned in an ultrasonic water bath for
5min. Specimens fabricated by the casting, milling or SLM
technique (0.5mm3mm25mm) were examined on the
3mm25mm surface. The examined surfaces were imaged
using a backscattered electron detector (BSE) under an accel-
erating voltage of 30kV and a beam current of 48A at a
working distance of 10mm. The elemental composition was
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Table 1 Brand names, elemental compositions and coefcients of thermal expansion (CTE) of the tested alloys, as
provided by the manufacturers.
Brand names Manufacturer Co Cr Mo Si Mn Fe
Okta-C Sae Dental Products
Inc. Bremerhaven,
Germany
61.6 30.0 6.5 0.8 0.8 N/A
ST2725G SINT-TECH, Riom,
France.
Bal (max 62.5) 29 5.5 <1 <1 <1
VI-COMP Dentsply, Elephant
Dental, Hoorn, The
Netherlands.
61.12.0 32.02.0 5.51.0 <1 <1 N/A
N/A, not available.
determined by EDX. EDX spectra were acquired from each
specimen using the area scan mode under an accelerating
voltage of 30kV, abeamcurrent of 48A, asampling windowof
430m430mand an acquisition time of 1000s. Moreover,
EDXspot analyses were performedunder these conditions ina
dispersed phase under mean atomic number contrast. Quan-
titative analysis of the acquired spectra was conducted using
INCA software (INCA Suite v 4.13) in a non-standard analysis.
2.4. XRD analysis
Three specimens from each group were ground using SiC
paper of up to 2000 grit, cleaned with acetone and subjected
to analysis using an XRD machine (D8 Advance, Bruker, MA,
USA) with an accelerating voltage of 40kV, a beam current of
40mA, a 2 angle scan range of 30110
, a scanning speed of
0.02
/s, a sampling pitch of 0.02
and a preset time of 1s.

2.5. Hardness
Vickers hardness (HV10) testing (Diatronic 2RC, Wolpert,
Germany) was performed in ve specimens of all groups,
with 12 measurements obtained per specimen under a load
of 10kg for 30s of dwell time. The average value of the 12
measurements was used to characterize the hardness of each
specimen.
2.6. Interfacial characterization
Four specimens fromeach group were equally divided in two
subgroups. Before the veneering procedure was initiated, the
surfaces of the specimens were ground with SiC paper of up
to 2000 grit, polished with diamond pastes up to 1m (DP
Paste, Struers) and cleaned in an ultrasonic bath for 10min
in 95% ethanol. The rst subgroup was fused with two layers
of opaque, followed by two layers of dentin and one layer of
dental porcelain (GC Initial MC, Europe N.V., Leuven, Belgium)
according to the manufacturers instructions (Table 2). The
second group was initially covered with bonding agent (GC
Initial INmetalbond) before the application of the opaque and
other layers. The specimens were then embedded in resin,
ground with SiC paper of up to 2000 grit and polished with
6m, 3mand 1mdiamond pastes (DP Paste, Struers). Fol-
lowing platinum sputter coating (JFC 1600 Auto Fine Coater,
Jeol), the metal ceramic interface was imaged using a BE
detector at a nominal magnication of 2000. For each speci-
men, anEDXspectrumwas acquiredfor the bulk of the opaque
or INmetalbond (indicated by the dotted rectangle in Fig. 4)
using an accelerating voltage of 30kV and a beam current
of 53A at a working distance of 10mm over an acquisi-
tion time of 200s. EDX line prole analysis was performed
across the interfaces of the two subgroups under an accel-
erating voltage of 30kV and a beam current of 48A at a
working distance of 10mm, a line prole scanning distance of
2.56m, a magnication of 50,000 and an acquisition time
of 1280s. The curves were smoothed using the local smooth-
ing technique with bi-square weighting and polynomial
regression.
2.7. Statistical analysis
The hardness results were statistically compared using one-
way ANOVA and HolmSidaks multiple comparison test
(=0.05).
3. Results
3.1. X-ray testing
Fig. 1 shows representative X-ray images inwhichgross poros-
ity was found at the center of the cast specimens, whereas no
porosity was detected for the MIL and SLM groups.
3.2. SEM-EDX characterization
BEI revealed the presence of a dispersed second phase with
a higher mean atomic number in the matrix of cast spec-
imens (Fig. 2A). Milled specimens also contained a second
phase with a higher mean atomic number relative to the
matrix and an even heavier phase located at the interface
between the second phase and the matrix (Fig. 2B). How-
ever, no contrast in mean atomic number was identied for
the SLM specimens (Fig. 2C). All groups demonstrated a ran-
dom distribution of small spherical pores, and this nding
was more profound in the cast group. Table 2 illustrates
the elemental composition of all groups together with the
composition of the matrix and dispersed phases after EDX
analysis. All groups showed similar values with regard to the
accuracy of the EDX analysis. The dispersed phase A
c
was
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Table 2 Firing schedules of the veneering procedure for GC Initial MC porcelain (according to the manufacturers
instructions).
Product name Pre-heating
temp. (
C)
Drying time
(min)
Heating rate
(
C/min)
Vacuum Final temp. (
C) Holding time
(min)
INmetalBond 550 6 80 Yes 980 1
Opaque 550 6 80 Yes 940 1
Dentin 580 6 55 Yes 900 1
Glaze 480 2 45 No 850 1
Fig. 1 Representative X-ray images of the (A) CST, (B) MIL and (C) SLMgroups. Porosity was identied only in the CST group.
enriched mainly in Mo and less in Cr, which was also the
case for the A
m
phase. In the MIL group, the B
m
was heavily
enriched in Mo but depleted in Cr relative to the matrix con-
tent. All of the dispersed phase primarily had low Co content
(Table 3).
3.3. XRD analysis
Following the XRD analysis, the diagrams recorded from all
groups were indexed as presented in Fig. 3. In addition to the
face-centered cubic (fcc) phase of Co and Cr, the hexagonal
close-packed (hcp) Co
3
Mo phase was identied in all speci-
mens. Additionally, Cr
7
C
3
and Cr
23
C
6
carbides were identied
in the CST and MIL groups.
3.4. Hardness
In total, 12 measurements of Vickers hardness were acquired
for the specimens of each dental alloy. The mean values
and the standard deviations were calculated as 32012HV,
2975HV and 37110HV for the CST, MIL and SLM groups,
respectively. Statistically signicant differences were found
among all the groups tested (p<0.05).
3.5. Interfacial characterization
Representative BEI from the interface of all materials tested
are presented in Fig. 4, and they show a well-formed and
dened interface between the CoCr alloy and the opaque or
INmetalbond. Image contrast revealed that the opaque is a
Fig. 2 Representative BE images of the microstructure observed in (A) cast, (B) milled and (C) SLM specimens. Note the
dispersion of a second phase in the cast and milled specimens (white contrast indicated with white arrows) and the
absence of such a phase in the SLM specimen. Precipitates of a third phase were also detected in the milled specimen (BM
in Fig. 2B). Porosity can also be observed in the images.
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Fig. 3 Indexed XRD diagrams of all groups included in the study. SLM showed only the presence of (Co,Cr) and Co
3
Mo
phases, in contrast to the CST and MIL groups, in which two Cr carbides were also identied.
Fig. 4 Representative BE images of the (A) metalINmetalbondopaque and (B) metalopaque interfaces. EDX area analyses
were performed as indicated on the images.
Table 3 Quantitative results of EDX analysis (wt%) of alloys (area analysis) and different phases (spot analysis) based on
the mean atomic contrast of BEI (Fig. 2). For the sake of clarity, the accuracy intervals of the EDX analysis are given only
for the alloy composition.
Element CST MIL SLM
Alloy M
c
A
c
Alloy M
m
A
m
B
m
Alloy
Co 59.9 [56.962.9] 62.7 46.9 59.1 [56.162.1] 60.2 47.9 43.2 62.7 [59.665.8]
Cr 32.2 [30.633.8] 31.7 35.8 33.1 [31.434.8] 33.3 37.9 26.9 29.2 [27.730.7]
Mo 6.2 [5.66.8] 4.3 15.3 6.0 [5.46.6] 4.9 12.3 28.2 6.3 [5.76.9]
Si 1.0 [0.81.2] 0.9 1.3 0.9 [0.41.3] 0.6 1.0 0.6 0.9 [0.41.3]
Mn 0.5 [0.20.7] 0.4 0.7 0.4 [0.20.6] 0.5 0.5 0.8 0.8 [0.41.2]
Fe 0.2 [0.10.3] 0.2 0.1 0.5 [0.20.7] 0.5 0.4 0.3 0.1 [0.10.2]
Table 4 EDX area analysis (wt%) of the INmetalbond and the opaque.
Material Element
O Si Ti Zr Fe Na Al K Ca Mg Zn
INmetalbond 22.9 19.4 29.2 12.3 1.7 3.7 3.4 6.6 0.8
Opaque 24.7 21.9 1.5 30.0 0.2 3.1 5.7 9.3 2.3 0.3 1.0
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Fig. 5 EDX line prole analysis performed across the interface between the alloy and the opaque (A, C and E) or
INmetalbond (B, D and F). The white horizontal line represents the scanning route. The plateau observed in the Cr prole is
indicated by an arrow.
multiphase material, whereas the INmetalbond exhibited a
matrix with a dispersed phase that had a higher mean atomic
number. The elemental composition of both materials as
determined by EDX analysis is presented in Table 4. INmetal-
bond showed increased Ti content relative to the opaque,
mainly at the expense of Zr content. The results of the EDX
line prole analysis, recorded across either the metalopaque
interface or the metal-INmetalbond interface, are presented
in Fig. 5. All probed elements demonstrated a steady decrease
(Co) or increase (Si, K and Ti) fromthe alloy toward the porce-
lain or INmetalbond. An exception to this general trend was
observed for the Cr prole line in the groups with opaque,
which demonstrated an obvious plateau at the interface, as
indicated by the arrows in Fig. 5A, C and E.
4. Discussion
This study focused on the microstructural and interfacial
characterization of CoCr PFMalloys fabricated using casting,
milling and selective laser sintering. All of these manu-
facturing processes are currently used for the production
of dental prosthetic restorations. Based on the data pre-
sented above, the null hypothesis must be rejected, as
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signicant dissimilarities were found among the groups
tested, apart from the interfacial distribution of metallic
elements at the metalceramic joint with or without INmetal-
bond.
Although great effort was invested in nding a single alloy
that could be used for the three manufacturing processes,
suchanalloy was not available at the time of this study. There-
fore, the best matching nominal compositions as presented
in Table 1 were selected from a large pool of commercially
available CoCr dental alloys. EDX results indicated similar
values for all elements among different groups within the rel-
ative internal error of the quantitative standardless analysis
(Table 2), although a slightly higher Co/Cr ratio was identied
for the SLM group relative to the rest of the alloys. Although
Fe was identied in all groups, it is only known to exist in
the nominal composition of the ST2724G alloy. Interestingly,
the presence of Fe in the nominal composition of the ST2724G
CoCr alloy has beenbothreported [9] and not reported [14,15].
An explanation for this inconsistency may be that the manu-
facturers slightly modied the formulations without changing
the brand name. Alternatively, the presence of these traces
may be attributed to the contamination of the raw materials
and/or contamination during the manufacturing process of
the alloys.
BEI demonstrated microstructural differences among the
tested groups. The CST group showed the typical cast struc-
ture of a CoCr dental alloy [2225], as the specimens were
composed of a matrix (M
c
) and a heavier dispersed phase
(A
c
) that occupy the interdendritic spaces. Although the den-
dritic structure was not clearly outlined, this magnication
was kept constant among the different groups for compar-
ison purposes. This phase was expected to be rich in the
heavier available elements, primarily Mo (Table 1), because of
its lighter contrast relative to the matrix in the BEI mode, and
this phenomenon was conrmed by EDX analysis (Table 2).
Because of its different composition and crystal structure, the
formation of this bulky phase is considered to be undesirable
because it increases the brittleness and deteriorates the cor-
rosion resistance of the alloy by removing Mo from the solid
solution [26]. A second phase (A
m
) with a higher mean atomic
number relative to the matrix (M
m
) was also observed in the
microstructure of the MIL group (Fig. 2B), similarly to the cast
material, but with a more bulky morphology. Similarly to the
CST group, A
m
demonstrated increased Mo and Cr content,
andanevenhigher Mo content was detectedinthe thirdphase
B
m
(Table 2), which agrees with previous observations in sim-
ilar alloys [26]. The formation of this phase, which preferably
nucleates and coarsens at the interface of the second phase
and the matrix, promotes the further depletion of Mo in the
matrix, which implies the deterioration of the corrosion resis-
tance [27]. Mo is also added to CoCr alloys to achieve a ner
grain structure, thereby enhancing the mechanical proper-
ties of the material [26]. This favorable effect is diminished
when Mo is segregated in Mo-rich compounds rather than
being dispersed within the matrix. In contrast to the CST and
MIL groups, no mean atomic contrast was revealed for the
SLM material a nding which is in agreement with a recently
published study [25]. This difference implies a completely
different solidication and/or thermomechanical history of
the tested groups [22,27,28].
XRD analysis results (Fig. 3) indicated that the microstruc-
ture of all groups consisted of the face-centered cubic (fcc)
phase, which mainly comprised Co and Cr which is in agree-
ment with a previous study [29]. As an allotropic element,
Co has a fcc crystal structure above temperatures of approx-
imately 417
C and a hexagonal crystal packing (hcp) below

this temperature, but in CoCr alloys, the fcc structure is
maintained at roomtemperature because of the lowfcc hcp
transformation rate. The fcc phase should be attributed to
the matrix of the microstructure for the CST and MIL groups
(Fig. 2Aand B), whereas the Co
3
Mo phase, which has also been
identied in previous studies of cast alloys [27,30] as a Mo-
rich compound (Table 2), should be attributed to the dispersed
phases A
c
and A
m
of the CST and MIL groups, respectively.
Although this phase was identied by XRD analysis in the
SLM group, no mean atomic number contrast was found in
BEI, possibly because of the rapid solidication of fused metal-
lic particles that led to a very ne phase size that was below
the resolutionof backscattered electronimaging. Additionally,
the previously found carbides [22] Cr
23
C
6
and Cr
7
C
3
were also
identied by XRD analysis only in the CST and MIL groups
(Fig. 3). Even when the manufacturer produces a raw mate-
rial with a lowC content, carbide formation may occur during
the manufacturing process and thus affect the nominal prop-
erties [24,26,28,3033] of the produced alloys. In addition to
the detected carbides, it is possible that other carbides could
have formed in the microstructure of the examined materi-
als [24,30], but the amount of these carbides is most likely
below the detection limit of the technique. The application of
advanced electron microscopy techniques, such as transmis-
sion electron microscopy (TEM), could provide further crucial
information, especially on the microstructural characteriza-
tion and the formation mechanismof the developed phases.
Despite the detrimental effect of internal porosity, which
is a common complication of the casting procedure for CoCr
alloys [34,35], the signicantly higher hardness observedinthe
CST group (32012HV) relative to the MIL group (2975HV)
may be attributed to the ner distribution of the dispersed
phase (Fig. 2). However, the increased hardness observed in
the SLM group (37110HV) could be attributed to the sinter-
ing technique, whichnot only diminishes undesirable porosity
but also provides a much more ne-grained structure [1]. This
is in agreement with a recently published study indicating
that SLMtechnique provides CoCr alloys with enhanced ulti-
mate tensile strengthandelongationcomparedto casting [29].
Additionally, the presence of residual stresses during sinter-
ing is another possible explanation for the increased hardness
in the SLM [36,37].
The surface of the three tested groups was intentionally
polished using a 1-m diamond paste prior to the veneering
procedure. Despite the manufacturers recommendations for
surface roughening before porcelain application, a at surface
is required to obtain a very small area for EDXline prole anal-
ysis (Fig. 5). In addition, the retained alumina fragments on
metallic surfaces after sandblasting [38] mask the real distri-
bution of Al and O at the interface. Interfacial analysis with
BE imaging revealed that both the opaque and INmetalbond
adhered well to the metallic substrates for all groups tested
(Fig. 4), thereby providing a continuous interface with the
substrate. In addition to the typical layering procedure with
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Fig. 6 Standard free energy of different reactions with O for Co, Cr, Si and Ti, commonly known as Ellinghams Diagrams.
A lower position reects higher chemical afnity of the element with O. Both axes have the same range for comparison
purposes.
opaque directly applied on the metallic surface, various prod-
ucts have beenintroduced to the market that claimto increase
either the bond strength or the esthetics of PFM restorations
[39]. Specically, INmetalbond is advertised as a material that
aims to block the escaping metal oxides and neutralize differ-
ences in the thermal expansion coefcient between porcelain
and metal. The application of this bonder is optional and
is recommended by the company for all precious and non-
precious PFM dental alloys.
The line prole analysis did not reveal any concentra-
tion gradient at the interface, but interestingly, the Cr prole
demonstrated a plateau at the interface for all groups covered
with opaque, but not with INmetalbond. An explanation for
this behavior may include the chemical afnity of the involved
elements to O. This information is provided by typical Elling-
ham diagrams presented in Fig. 6 [40], which show the free
energy of a given oxide as a function of temperature. A lower
position reects higher chemical afnity of an element to O
and thus a higher tendency to react with O. Given that Cr has
a higher chemical afnity to OthanCo and Mo (the latter is not
shown in Fig. 6), it reacts rst, thereby increasing the contribu-
tion of Cr compounds at the interface. It should be mentioned
that even if the other metal reacts rst because of kinetic rea-
sons, Cr ions can still reduce the oxides of the other metals
based on the metallothermic reaction, in which a metal with a
higher chemical afnity to O(M
H
) reduces the oxides of metals
with a lower afnity to O (M
L
) based on the following general
formula:
(M
H
) + (M
L
)xO
y
(M
H
)O
y
+x(M
L
)
Surprisingly, this behavior vanished when the INmetal-
bond was applied for all groups tested, which may be
associated with a higher chemical afnity of Ti with oxygen,
as Ti is the predominant element of INmetalbond. Of course,
this mechanism requires that Ti be capable of reacting with
O or participating in metallothermic reactions. In contrast,
although Si has a similar chemical afnity to O as Ti, it is
widely known that Si is anchored in the glassy matrix as an
oxide [41], and thus its capability for further reaction is elim-
inated. Although this thermodynamic approach agrees with
the data presented above, it is worthwhile to note that these
calculations represent the reaction of pure elements with O
and must be corrected when they are used for alloying ele-
ments in different alloys. However, such data are not available
and their calculation requires extensive research. In conclu-
sion, it is clear that the application of INmetalbond affects the
interfacial distribution of involved elements, and therefore its
effect should be further examined.
These ndings regarding microstructural properties may
have clinical implications. Mechanical properties (i.e., the
fatigue resistance of dental clasps), electrochemical proper-
ties and other properties may be altered by microstructural
changes, and further research is thus required in this eld,
especially for the recently introduced SLM technology. How-
ever, no differences were found for the elemental distribution
of the probed elements at the metalporcelain interface,
which agrees with previous data that showed no difference
in bond strength between cast and laser-sintered structures
[8,18].
Given that the microstructure and hardness were signif-
icantly different in the SLM group, further differences in
the clinical behavior of prosthetic restorations manufactured
using this technique are anticipated. SLM technology has
recently been introduced in the dental eld, and a vast spec-
trumof factors should be tested and/or optimized to increase
its efcacy in the production of metallic dental restorations.
5. Conclusions
Within the limitations of this study, the following conclusions
can be derived:
CoCr dental alloys fabricated via casting, milling or SLM
techniques show signicant differences in microstructure
ARTICLE IN PRESS
and hardness but not at the elemental distribution level of
metalceramic interface.
The application of INmetalbond has a profound effect on
the elements at the interface between the metal and the
opaque porcelain.
Acknowledgments
This study has been funded by a research grant (RGP-VPP-
206) fromthe Research Group Program, Deanship of Scientic
Research, King Saud University, Riyadh, Saudi Arabia.
The authors would like to thank Phenix Systems and Mr
Briakos Dental Lab for the manufacturing of metallic speci-
mens.
r e f e r e n c e s
[1] van Noort R. The future of dental devices is digital. Dent
Mater 2012;28:312.
[2] Willer J, Rossbach A, Weber HP. Computer-assisted milling of
dental restorations using a new CAD/CAMdata acquisition
system. J Prosthet Dent 1998;80:34653.
[3] Quante K, Ludwig K, Kern M. Marginal and internal t of
metalceramic crowns fabricated with a new laser melting
technology. Dent Mater 2008;24:13115.
[4] Traini T, Mangano C, Sammons RL, Mangano F, Macchi A,
Piattelli A. Direct laser metal sintering as a new approach to
fabrication of an isoelastic functionally graded material for
manufacture of porous titaniumdental implants. Dent
Mater 2008;24:152533.
[5] Miyazaki T, Hotta Y. CAD/CAMsystems available for the
fabrication of crown and bridge restorations. Aust Dent J
2011;56(Suppl. 1):97106.
[6] Witkowski S, Komine F, Gerds T. Marginal accuracy of
titaniumcopings fabricated by casting and CAD/CAM
techniques. J Prosthet Dent 2006;96:4752.
[7] Alt V, Hannig M, Wostmann B, Balkenhol M. Fracture
strength of temporary xed partial dentures: CAD/CAM
versus directly fabricated restorations. Dent Mater
2011;27:33947.
[8] Akova T, Ucar Y, Tukay A, Balkaya MC, Brantley WA.
Comparison of the bond strength of laser-sintered and cast
base metal dental alloys to porcelain. Dent Mater
2008;24:14004.
[9] Ucar Y, Akova T, Akyil MS, Brantley WA. Internal t
evaluation of crowns prepared using a new dental crown
fabrication technique: laser-sintered CoCr crowns. J
Prosthet Dent 2009;102:2539.
[10] Tian XY, Gunster J, Melcher J, Li DC, Heinrich JG. Process
parameters analysis of direct laser sintering and post
treatment of porcelain components using Taguchis method.
J Eur CeramSoc 2009;29:190315.
[11] Williams RJ, Bibb R, Eggbeer D, Collis J. Use of CAD/CAM
technology to fabricate a removable partial denture
framework. J Prosthet Dent 2006;96:969.
[12] Tara MA, Eschbach S, Bohlsen F, Kern M. Clinical outcome of
metalceramic crowns fabricated with laser-sintering
technology. Int J Prosthodont 2011;24:468.
[13] Ortorp A, Jonsson D, Mouhsen A, Vult von Steyern P. The t
of cobaltchromiumthree-unit xed dental prostheses
fabricated with four different techniques: a comparative
in vitro study. Dent Mater 2011;27:35663.
[14] Castillo-Oyague R, Osorio R, Osorio E, Sanchez-Aguilera F,
Toledano M. The effect of surface treatments on the
microroughness of laser-sintered and vacuum-cast base
metal alloys for dental prosthetic frameworks. Microsc Res
Tech 2012;75:120612.
[15] Castillo-de-Oyague R, Sanchez-Turrion A, Lopez-Lozano JF,
Albaladejo A, Torres-Lagares D, Montero J, et al. Vertical
mist of laser-sintered and vacuum-cast implant-supported
crown copings luted with denitive and temporary luting
agents. Med Oral Patol Oral Cir Bucal 2012;17:e6107.
[16] Oyague RC, Sanchez-Turrion A, Lopez-Lozano JF, Montero J,
Albaladejo A, Suarez-Garcia MJ. Evaluation of t of
cement-retained implant-supported 3-unit structures
fabricated with direct metal laser sintering and vacuum
casting techniques. Odontology 2012;100:24953.
[17] Oyague RC, Sanchez-Turrion A, Lopez-Lozano JF,
Suarez-Garcia MJ. Vertical discrepancy and microleakage of
laser-sintered and vacuum-cast implant-supported
structures luted with different cement types. J Dent
2012;40:12330.
[18] Xiang N, Xin XZ, Chen J, Wei B. Metalceramic bond strength
of CoCr alloy fabricated by selective laser melting. J Dent
2012;40:4537.
[19] Reclaru L, Ardelean L, Rusu L, Sinescu C. CoCr material
selection in prosthetic restoration: laser sintering
technology. Solid State Phenom2012;188:4125.
[20] Castillo-Oyague R, Lynch CD, Turrion AS, Lopez-Lozano JF,
Torres-Lagares D, Suarez-Garcia MJ. Mist and microleakage
of implant-supported crown copings obtained by laser
sintering and casting techniques, luted with glass-ionomer,
resin cements and acrylic/urethane-based agents. J Dent
2013;41:906.
[21] Iseri U, Ozkurt Z, Kazazoglu E. Shear bond strengths of
veneering porcelain to cast, machined and laser-sintered
titanium. Dent Mater J 2011;30:27480.
[22] Hero H, Syverud M, Gjonnes J, Horst JA. Ductility and
structure of some cobalt-base dental casting alloys.
Biomaterials 1984;5:2018.
[23] Qiu J, Yu WQ, Zhang FQ, Smales RJ, Zhang YL, Lu CH.
Corrosion behaviour and surface analysis of a CoCr and
two NiCr dental alloys before and after simulated porcelain
ring. Eur J Oral Sci 2011;119:93101.
[24] Ramirez LE, Castro M, Mendez M, Lacaze J, Herrera M,
Lesoult G. Precipitation path of secondary phases during
solidication of the Co25.5%Cr5.5%Mo0.26%C alloy. Scr
Mater 2002;47:8116.
[25] Xin XZ, Chen J, Xiang N, Wei B. Surface properties and
corrosion behavior of CoCr alloy fabricated with selective
laser melting technique. Cell BiochemBiophys 2013,
http://dx.doi.org/10.1007/s12013-013-9593-9.
[26] Karpuschewski B, Pieper HJ, Krause M, Doring J. CoCr is not
the same: CoCr-blanks for dental machining. In: Schuh G,
Neugebauer R, Uhlmann E, editors. Future trends in
production engineering. Berlin, Heidelberg: Springer-Verlag;
2013. p. 26174.
[27] Matkovic T, Matkovic P, Malina J. Effects of Ni and Mo on the
microstructure and some other properties of CoCr dental
alloys. J Alloys Compd 2004;366:2937.
[28] Yoda K, Suyalatu, Takaichi A, Nomura N, Tsutsumi Y, Doi H,
et al. Effects of chromiumand nitrogen content on the
microstructures and mechanical properties of as-cast
CoCrMo alloys for dental applications. Acta Biomater
2012;8:285662.
[29] Takaichi A, Suyalatu, Nakamoto T, Joko N, Nomura N,
Tsutsumi Y, et al. Microstructures and mechanical
properties of Co29Cr6Mo alloy fabricated by selective laser
melting process for dental applications. J Mech Behav
Biomed Mater 2013;21:6776.
[30] Podrez-Radziszewska M, Haimann K, Dudzikski W,
Morawska-Soltysik M. Characteristic of intermetallic phases
in cast dental CoCrMo alloy. Arch Foundry Eng 2010;10:516.
ARTICLE IN PRESS
[31] Ishida K, Nishizawa T. The CoCr (cobaltchromium) system.
Bull Alloy Phase Diagr 1990;11:35770.
[32] Gupta KP. The CoCrMo (cobaltchromiummolybdenum)
system. J Phase Equilib Diffus 2005;26:8792.
[33] Rodrigues WC, Broilo LR, Schaeffer L, Knornschild G,
Espinoza FRM. Powder metallurgical processing of
Co28%Cr6%Mo for dental implants: physical, mechanical
and electrochemical properties. Powder Technol
2011;206:2338.
[34] Eisenburger M, Addy M. Radiological examination of dental
castingsa review of the method and comparisons of the
equipment. J Oral Rehabil 2002;29:60914.
[35] Dharmar S, Rathnasamy RJ, Swaminathan TN. Radiographic
and metallographic evaluation of porosity defects and grain
structure of cast chromiumcobalt removable partial
dentures. J Prosthet Dent 1993;69:
36973.
[36] Simchi A, Pohl H. Effects of laser sintering processing
parameters on the microstructure and densication of iron
powder. Mater Sci Eng A: Struct Mater Prop Microstruct
Process 2003;359:11928.
[37] Shiomi M, Osakada K, Nakamura K, Yamashita T, Abe F.
Residual stress within metallic model made by selective
laser melting process. CIRP Ann Manuf Technol
2004;53:1958.
[38] Al Jabbari YS, Zinelis S, Eliades G. Effect of sandblasting
conditions on alumina retention in representative dental
alloys. Dent Mater J 2012;31:24955.
[39] Chakmakchi M, Eliades G, Zinelis S. Bonding agents of low
fusing cpTi porcelains: elemental and morphological
characterization. J Prosthodont Res 2009;53:16671.
[40] DoITPMS. Dissemination of IT for the promotion of
materials science. University of Cambridge.
http://www.doitpoms.ac.uk/tlplib/ellingham diagrams/
interactive.php [accessed 22.02.13].
[41] Ban S, Matsuo K, Mizutani N, Tanikawa H, Kaikawa K,
Hasegawa J. Effect of cooling condition on leucite crystals in
dental porcelains. Dent Mater J 1999;18:13743.

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Please cite this article in press as: Al Jabbari YS, et al.

C and cast with VI-COMP alloy at 1450

C; the laser systemhadthe ability toweld

/s, a sampling pitch of 0.02

and a preset time of 1s.

C and a hexagonal crystal packing (hcp) below

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