Materials Science and Engineering A 454–455 (2007) 178–182

Pure titanium casting into titanium-modified calcia-based and

magnesia-based investment molds
C.C. Hung a,∗ , P.L. Lai a , C.C. Tsai b , T.K. Huang c , Y.Y. Liao c
a Graduate Institute of Dental Science, Department of Prosthodontics, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 807, Taiwan
b Department of Periodontics, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 807, Taiwan
c Graduate Institute of Dental Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 807, Taiwan

Received 20 July 2006; received in revised form 1 November 2006; accepted 3 November 2006

Abstract
Calcia is the most stable oxide for molten titanium at high temperature. In this study, pure titanium casting into calcia- and magnesia-based
investments was investigated. Experimental results show that adding the proper amount of titanium powder into calcia- and magnesia-based
investments can increase the thermal expansion value, at 800 ◦ C, of both investments. Pure titanium castings in the calcia-based group have
better expression at the interface reactivity and the VH. However, castings in magnesia-based group have better results for the investing and the
dimensional accuracy.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Pure titanium; Calcia investment; Magnesia investment; Casting

1. Introduction temperatures for investment can give enough thermal expansion

Since titanium and its alloys have a great specific strength, the
improvement of the mechanical properties is of growing impor-
tance in the aircraft and space industry [1]. Pure titanium is
also increasingly used in dental applications because of its high
corrosion resistance, excellent biocompatibility, and adequate
mechanical properties. Titanium contamination with oxygen,
hydrogen and nitrogen during the casting procedure will result in
alterations of its physical and mechanical properties. Its reactiv-
ity with oxygen at elevated temperatures and low density make
the casting process difficult. The surface of titanium castings
exhibits a layered structure as a result of a reaction with the
mold materials. Because of titanium’s high reactivity with sil-
ica investments, specially formulated mold materials containing
alumina, magnesia, yttria, zirconia and calcia were developed
[2–8]. To achieve high quality dental casting, the difference
between the dimensional accuracy and the surface reaction of
pure titanium should not be large [9]. The relatively low mold
temperatures for investment do not give enough mold expansion
to compensate for metal shrinkage. The relatively high mold
∗ Corresponding author. Tel.: +886 7 3804437; fax: +886 7 3804437.
E-mail address: yuchali@ms21.hinet.net (C.C. Hung).
but produce large surface oxidation [1]. From the viewpoint of
the free-energy diagram of the titanium–oxygen system, calcia
is the most stable oxide for molten titanium at high temperature
but it has not been popular as a refractory material. Since calcia
is hydrated easily [7] and is difficult to manipulate, its use as
a dental refractory investment has been negligible. A high cor-
relation coefficient was found between dimensional accuracy
and thermal expansion value in titanium crown making [10].
Because of the small setting expansion and thermal shrinkage
during heating of the calcia investment, utilizing a metal oxide
to compensate for the shrinkage was needed [11]. Takahashi et
al. [12] reported that using the titanium powder as an expanding
agent could increase the thermal expansion of a calcia invest-
ment at 1000 ◦ C. However, a burn-out furnace over 1000 ◦ C is
not commonly found in dental laboratories. From the XRD anal-
ysis [13,14], when the firing temperature was over 900 ◦ C, the
␣-Ti intensity was substantially reduced and the TiO2 intensity
was dramatically increased. Takahashi et al. [7] also reported
that using the titanium powder in a calcia investment could
compensate for the casting shrinkage of titanium at 800 ◦ C. To
summarize, the main problems of calcia refractory material were
insufficient thermal expansion, difficult operation, and exagger-
ative mixing reaction. The aim of this study was to investigate
the accuracy of pure titanium casting by adding titanium powder

0921-5093/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2006.11.044
 C.C. Hung et al. / Materials Science and Engineering A 454–455 (2007) 178–182 179

to calcia- and magnesia-based investment molds. The dimen-

sional accuracy and interfacial reactivity were used to evaluate
the suitability of these castings.

2. Experimental procedure

2.1. Experimental investments

The calcia-based investment group consisted of calcia pow-

der (CaO, FCA-8A, #325 Pass, Tateto Chemical Co., Kobe,
Japan) as a refractory filler and 0–8 wt% titanium powder (Ti,
Fig. 1. Dimensional accuracy of a cast crown is expressed by the discrepancy
TMP-350, <45 ␮m, Amagasaki Co., Sumitomo, Japan) as an (dy–dx) measured on its wax pattern and the casting on the same die.
expanding agent. The blending of the calcia-based investment
and titanium powder was done prior to being hand mixed with
cially, pure titanium (7 g, JIS grade 2, Ohara Co., Osaka,) was
methanol in a rubber bowl. Methanol (purity of 99.5 wt%,
cast into these molds using an automatic argon-casting machine
Nihon Shiyaku Co., Osaka, Japan) was used as a mixing agent,
(Castmatic-S, Iwatani Co., Osaka, Japan). An argon gas pressure
the methanol to powder ratio used was 0.23. To prevent the
of 1.8 kgf/cm2 and a current of 250 A were chosen. After 20 s of
volatilization of methanol and control the setting reaction, the
melting time, the molten titanium was pressed into the evacuated
molds were stored in a refrigerator for 20 h [7]. The magnesia-
mold, the argon supply continued for about 60 s after filling the
based investment group (Selevest CB, Selec Co., Osaka, Japan)
mold with titanium. Five specimens were cast for each different
was also modified by adding 0–8 wt% titanium powder as an
tested group. Casting specimens were sandblasted using 50 ␮m
expanding agent. The blending of the magnesia-based invest-
Al2 O3 . The definitions of unsuccessful castings include: incom-
ment and titanium powder was done prior to being mixed with
plete casting, rounded short margins and undesirable porosity.
water under a vacuum mixer. All procedures were done under
Dimensional accuracy in casting specimens was measured on
the conditions of 23 ± 2 ◦ C and 50 ± 10% relative humidity.
the same metal die using a stereomicroscope (Nikon SM-2T,
Tokyo, Japan). The distance separating the margin of the wax
2.2. Thermal expansion measurement of investments
inlay and the shoulder of the metal die (X) was measured at four
fixed points. All castings were seated under a load of 5 kgf and
The same mixing method was used for both TE measurement
the distance separating the margin of the inlay and the shoulder
and inlay casting. The recommended L/P ratio for calcia-based
of the metal die (Y) was measured at the same four fixed points
investment was 0.23 wt% and for magnesia-based investment
as the wax pattern. The dimensional accuracy was expressed
was 0.2 wt%. TE measurements were conducted on cylindrical
by the discrepancy of the two measurements (X–Y) for each
specimens (10 mm in diameter and 50 mm in height). Investment
point. One-way ANOVA and Tukey’s HSD test were used to
mixes were poured into copper molds and after 1 h the specimens
analyze the difference between the titanium powder ratio and
were removed from the molds and then dried for 1 day. An auto-
the dimensional accuracy of the MOD inlay.
matic TE laser-recording machine (TEM-1000, Pantos, Nippon
Co., Japan) was used to measure the TE of the investments. The
specimens were heated to 800 ◦ C at a rate of 6 ◦ C/min and cooled 2.4. Microhardness measurement of castings
to 200 ◦ C at the same rate. Three specimens were measured for
each condition. One-way ANOVA and Tukey’s HSD were used Sprues of MOD castings were cut horizontally, 3 mm from
to analyze the difference between the titanium powder ratio and the attachment point. The exposed cross-section was mounted
TE of investments. in epoxy resin and polished with 600 mesh emery paper and
0.05 ␮m alumina particles on a cloth-polishing wheel. The
2.3. Dimensional accuracy measurement of the castings microhardness of these specimens was measured from the outer
surface at 40 ␮m intervals using a Vickers microhardness inden-
Wax patterns for MOD inlays were made using a tapered ter (MTX-50, Matsuzawa Seiki Co., Japan) at 200 gf load.
metal die (8 mm in diameter, 7 mm in height and 2 mm in
thickness) (Fig. 1). Wax patterns were invested in casting 2.5. Interface oxidation evaluation of castings
rings (36 mm diameter, 46 mm in height) with one sheet of
kaowool liner (1 mm thickness), and a sprue (3 mm diameter). Sprues of MOD castings were cut horizontally 5 mm from
The invested molds were burned out in a programmed electric the attachment point. The exposed cross-section was mounted
furnace at a rate of 3 ◦ C/min for the calcia-based group and in epoxy resin and polished with 600 mesh emery paper and
6 ◦ C/min for the magnesia-based group. The mold temperature 0.05 ␮m alumina particle on a cloth-polishing wheel. The
of modified calcia-based group and the magnesia-based group composition of the interface surface was detected by energy dis-
were heated to 800 ◦ C, heat-soaked for 3 h, and cast at 800 ◦ C. persive X-ray analysis (EDX) and backscattered electron image
The melting temperature of pure titanium is about 1680 ◦ C, (BEI) of electron probe microanalyzer (EPMA; JXA-8900R,
the mold temperature is at 800 ◦ C during casting. Commer- Japan).
180 C.C. Hung et al. / Materials Science and Engineering A 454–455 (2007) 178–182
Fig. 2. Thermal expansion curves for calcia-based group with titanium powder.
3. Results
3.1. Thermal expansion
Maximal thermal expansion of both molds occurred at about
800 ◦ C, therefore, the mold casting temperature was set at 800 ◦ C
to compensate for titanium shrinkage. The thermal expansion
curves of the calcia-based group are shown in Fig. 2. The mean
TE values of the calcia-based modified group with 0, 2, 4, 6
and 8 wt% titanium powder were −0.87, −0.37, 0.18, 1.37 and
2.29% at 800 ◦ C, respectively. The thermal expansion of calcia-
based molds without titanium powder was −0.8% at 800 ◦ C
and those with titanium powder showed a rapid expansion at
800 ◦ C. One-way ANOVA indicated that titanium powder ratio
had significantly different to TE values of the calcia-based group
(p < 0.05). The TE curves of the magnesia-based group are
shown in Fig. 3. The mean TE values of magnesia-based modi-
fied group with 0, 2, 4, 6, and 8 wt% titanium powder were 0.98,
1.29, 1.57, 1.78 and 2.05% at 800 ◦ C, respectively. The thermal
expansion of magnesia-based molds with and without titanium
powder were shown to have negative values before 550 ◦ C, but
rapid expansion over 550–650 ◦ C was obtained by the zirconium
component. One-way ANOVA indicated that titanium powder
ratio had also significantly different to TE values of magnesia-
based group (p < 0.05). The cooling behavior of the magnesia
molds is more stable than calcia molds.
Fig. 3. Thermal expansion curves for magnesia-based group with titanium
powder.
Fig. 4. Dimensional accuracy for calcia- and magnesia-based group with tita-
nium powder. Each column represents the mean and standard deviation.
3.2. Dimensional accuracy
Mean dimensional accuracy of the MOD inlays is shown
in Fig. 4. The original calcia-based group had the largest
mean dimensional accuracy, 104.83 ± 32.97 ␮m at 800 ◦ C.
The magnesia-based group with 8 wt% titanium powder had
the smallest mean dimensional accuracy, 23.25 ± 6.33 ␮m at
800 ◦ C. One-way ANOVA and Tukey’s HSD tests indicated that
titanium powder ratio had significantly different dimensional
accuracy of both groups (p < 0.05).
3.3. Microhardness
Vickers hardness (VH) changes in titanium castings from the
outer to inner surfaces are shown in Fig. 5. Vickers hardness
decreased as titanium powder ratio increased in both groups.
The magnesia and calcia molds with 6–8 wt% titanium powder
had significantly decreased VH, especially, the calcia groups.
3.4. Interface oxidation
The EPMA (BEI) of the interface oxidation of castings is
shown in Fig. 6. The castings from the calcia-based investment
had a thinner oxidation zone than the magnesia-based invest-
Fig. 5. Microhardness changes in titanium castings for calcia- and magnesia-
based with titanium powder from outer to inner surface.
 C.C. Hung et al. / Materials Science and Engineering A 454–455 (2007) 178–182
Fig. 6. The backscattered electron image (BEI) of titanium castings interfacial oxidation zone (magnification: 15,000×).
ment castings. The 6 wt% titanium-modified calcia group had
the thinnest oxidation zone.
4. Discussion
Sufficient thermal expansion of the investment is critical
to the marginal accuracy of casting. Instead of the conven-
tional dial gauge device, the same automatic laser-recording
TE machine [14] was used, which can detect a 1 ␮m expan-
sion. Takahashi et al. [7] reported that a calcia-based investment
with 6.1 wt% titanium powder expanded 1.7% during 2 h heat-
ing at 800 ◦ C. Miyazaki et al. [15] reported that calcia-based
investment with 8.8 wt% titanium powder expanded 1.7% at
1000 ◦ C. In this study, the calcia-based investment had the max-
imum TE 1.88% at 375 ◦ C but the TE decreased to −0.87%
at 800 ◦ C. While the calcia-based investment with 8 wt% tita-
nium powder expanded 2.29% during 3 h heat-soaking at 800 ◦ C,
meanwhile the magnesia-based investment with 8 wt% titanium
powder expanded 2.05% during 3 h heat-soaking at 800 ◦ C. TE
values were significantly affected (p < 0.05) as titanium powder
increased for these two testing groups.
Nishimura et al. [16] estimated that the casting shrinkage of
the titanium crown was approximately 1.8–2.0%. Even though
the expansion of the calcia-based group with 8 wt% titanium
181
powder can compensate for the titanium casting shrinkage, these
molds seem to lack sufficient firing strength and manipulative
stability. Takahashi et al. [12] reported that the calcia–methanol
mold was sealed in a small container and stored in a refrigera-
tor for 20 h to prevent the exaggerative reaction. In this study,
we followed this method, but the complete casting rate of the
calcia-based group was only 60%. The casting failures included
incomplete casting and open rounded margins. Typically, molten
titanium is cast into mold that have been preheated (<800 ◦ C) or
are at room temperature [2,14]. The vast difference between the
mold and melting temperature causes rapid cooling and solid-
ification of the titanium [9,14]. Therefore, the pure titanium
casts were made in high temperature molds (800 ◦ C) in this
study to reduce the risk of incomplete casting. Christensen [17]
reported that the clinically accepted maximal marginal discrep-
ancy was under 50 ␮m. The original calcia-based group had the
largest marginal discrepancy (104.83 ± 32.97 ␮m), even though
the marginal discrepancy could be improved by 8 wt% tita-
nium powder (76.38 ± 25 ␮m) but all of these groups were not
accepted in clinical standardization. Compared with the calcia-
based investment, the magnesia-based investment was easier to
manipulate and had sufficient firing strength. The marginal dis-
crepancy of the magnesia-based investment could be improved
by titanium powder and all of these were accepted in stan-
182 C.C. Hung et al. / Materials Science and Engineering A 454–455 (2007) 178–182
dardization, especially in the 8 wt% titanium powder group
(23.25 ± 6.33 ␮m).
A hardness layer [3,4,8] called the ␣-case in titanium cast-
ing usually results from the reaction of molten titanium with
the investment material. Miyazaki et al. [11] reported that tita-
nium cast into a calcia–methanol mold with titanium powder
at 1000 ◦ C had about a 250 ␮m reaction layer. Takahashi et
al. [7] also reported that the titanium casting obtained from
a calcia mold at 800 ◦ C showed an excellent surface. In this
study, the calcia-based group with or without titanium powder
showed an excellent smooth surface compared to the magnesia-
based group at 800 ◦ C. The EPMA (BEI) showed the titanium
casting obtained from the calcia-based group with or without
titanium powder had the thinner uniform oxidation zone than
magnesia-based group. The calcia-based group with 8 wt% tita-
nium powder showed the thinnest oxidation zone (120 ␮m).
The VH of the original calcia-based group is higher than that
of the original magnesia-based group (p > 0.05). When titanium
powder is added there is more effective reduction of VH val-
ues for the calcia-based group compared to the magnesia-based
group (p < 0.01). The mold temperature and casting tempera-
ture are important parameters, which affect the extent of surface
hardening beneath the investment and casting interface. The for-
mation of these hard, brittle reaction layers can affect the surface
finish of the prosthesis. The magnesia and calcia molds without
titanium powder had the highest VH (VH 470) at the interface
area. The magnesia and calcia molds with 6–8% titanium powder
had significantly decreased VH (especially, the calcia groups,
VH 250–270). It is preferable to access the accuracy of castings
without excess surface finish and polish.
In conclusion, calcia is a more stable oxide than magnesia,
its surface oxidation is better than magnesia. Because of the
small total expansion (SE + TE) of the calcia, the expansion
was improved by titanium powder. In this study showed that
a proper amount (6–8 wt%) of titanium powder added into both
calcia- and magnesia-based investments could increase the ther-
mal expansion rate. Titanium casting obtained from calcia-based
groups had better results in the interfacial surface reaction, but
the low-dimensional accuracy is still an issue. Titanium cast-
ing obtained from magnesia-based groups had better results in
manipulation procedures. How to develop a calcia dominant
refractory investment for pure titanium casting, which combines
the character of calcia and magnesia refractory is the object of
future study.
Acknowledgments
The TEM-1000 equipment used in this study was supplied
by Osaka University, Japan. The financial support from NSC
research grant NSC89-2314-B037-054 was greatly appreciated.
The authors are grateful to Theodore Hsu, Eric Huang and
Yuchali Lu for their help on reviewing and editing this article.
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