Dental Materials Journal 2009; 28(3): 301306 Original Paper

Properties of a gypsum-bonded magnesia investment using a K2SO4 solution for titanium casting
 Fazal REZA1, Yukimichi TAMAKI2, Hidekazu TAKAHASHI1, Naohiko IWASAKI1 and Takashi MIYAZAKI2
1

Advanced Biomaterials, Department of Restorative Sciences, Division of Oral Health Sciences, Graduate School, Tokyo Medical and Dental University, 1-5-45 Yushima, Bunkyo-ku, Tokyo 113-8549, Japan. 2 Department of Oral Biomaterials & Technology, Showa University School Dentistry, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan Corresponding author, Fazal REZA; E-mail: reza.abm@tmd.ac.jp

The purpose of the study was to investigate the effects of a K2SO4 solution on the improvement of the properties of an experimentalmagnesia-basedgypsum-bondedinvestment. ThecharacteristicsoftheexperimentalinvestmentwithdifferentratiosofaK2SO4solutionwereasfollows:settingtime ranged from 34 to 152 minutes, green and fired compressive strengths were approximately 2.15 to 5.81 MPa and 1.63 to 2.45 MPa, respectively; thermal expansion was 0.38 to 0.47% at 700C, which did not show any significant differences due to the concentrationoftheK2SO4 solution. Titanium casting could be obtained using the experimental investment mixed with a 1% K2SO4solution,andthereactionlayerthicknessofthecastingwaslessthan200m. The results suggest that the experimental investment mixed with 1% K2SO4showedacceptablephysicalpropertiesand castingcharacteristicsfortitaniumcasting.

Keywords:Titanium,Gypsum-bondedinvestment,K2SO4 Received Oct 3, 2008: Accepted Dec 2, 2008

INTRODUCTION Titanium has gained popularity in the field of prosthodontics because of its excellent biocompatible property.  The most common fabricating process of dental prostheses using dental alloys has been the lost-wax casting method.  However, titanium casting for prostheses still has several problems due to its reaction with mold materials and its undesired surface reaction layer1,2). Therefore, searching for an appropriateinvestmentmaterialfortitaniumcasting hasbeenofupmostimportance. Gypsum-bonded investments have been widely used in dentistry and possess some advantages such as easy operation, relatively large setting expansion, and adequate green and fired strengths. However, gypsum-bonded investments is not suitable for high fusing casting alloys due to the decomposition of gypsum at around 1000 to 1200C or at 600 to 700C when carbon exists3,4).  Gypsum-bonded investments using magnesia and alumina as a refractory have  been reported to be applicable for titanium casting5).  Moreover, magnesia-based gypsum-bonded investments could be used for titanium casting. Regarding the magnesia-based gypsum-bonded investment for titanium casting, the gypsum content of 10 mass% showed good performance except for a long setting time6).  Several chemicals have been suggestedtoacceleratethesettingofgypsum-bonded investments.  The most commonly used accelerator

for this purpose is potassium sulfate.  Remarkable effects on setting time have been reported using potassiumsulfatesolutioninthemixingliquidofthe gypsum-bondedsilicainvestment7,8).Ithasalsobeen reported that the setting time of gypsum  bonded alumina magnesia investments decreases significantly when mixed with K2SO49). The purpose of this study was to improve the properties of the experimental magnesia-based gypsum-bonded investment using several concentrations of a K2SO4 solution and to evaluate thecastingusingthisinvestment. MATERIALS AND METHODS Experimental investment and mixing The experimental investment was composed of magnesia(#330meshpass,Tateho,Hyogo,Japan)as a refractory material and dental stone (alpha hemi hydrate gypsum, Noritake, Nagoya, Japan) as a binder material. The gypsum content of 10 mass% and the powder to the liquid ratio of 100 g/20 ml were used in the present study according to our previous report6).  Four concentrations of K2SO4 (grade1, Wako Pure Chemical Industries; Osaka, Japan) solutions (0, 1, 2, 3, and 5 mass%) were prepared; the investment was hand mixed for 30 seconds and for another 30 seconds with a mixing machine(Multivac,Degussa,Hanau,Germany).

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Dent Mater J 2009; 28(3): 301306 Japan) with Cu-K radiation, a fixed divergence slit anda2/minscanningspeed. Castability and Micro Vickers hardness of titanium casting A wax pattern of 25  25-mm (Grids, perforated RN III casting, Dentaurum, Ispringen, Germany) was used for evaluating castability of titanium11).  The experimental investment mixed with a 0% and a 1% K2SO4 solution was used for this evaluation.  A casting wax (Ready casting wax No R25, GC) was  used as the sprue; the diameter of the sprue was 2.5 mm and the height was 4 mm.  The pattern was invested and heated in the aforementioned manner.  Commercial pure titanium ingots (31g, Morita, Tokyo, Japan) were used for the casting procedure with a gas pressure and centrifugal casting machine (Vulcan T; Shofu, Kyoto, Japan) at a casting temperature of 200C. Three castings with a 0% K2SO4 solution and five castings with a 1% K2SO4 solution were obtained.  Castability was evaluated usingthefollowingformula: Castability= Number of completely cast holes 100 Total number of holes in wax pattern Castings obtained from the 1% K2SO4 solution werecutatthecenterofthesprueandcleanedwith asteamcleaner.Thespruewasembeddedinacrylic resin, consecutively polished with a polishing machine (Diarap ML150P, Maruto, Tokyo, Japan) using a diamond pad (600 and 1000), and finally polished with a polishing machine (Union Kogaku, GP 102, Tokyo, Japan) using aluminum oxide slurry (0.06m,N300;MarumotoKogyo,Tokyo,Japan). Vickers hardness (Hv) of the casting was measuredfrom50to300mindepthfromtheouter surface and at the center of each specimen to evaluate the reaction layer thickness.  A micro Vickers tester (MVK-H2 Akashi, Kanagawa, Japan) under a load of 100-gf and a duration time of 15 seconds was used for the measurement.   Five titaniumcastingswereexamined. Statistical analysis The obtained data were analyzed using one-way analysis of variance (ANOVA) and compared among groups by Tukeys comparison post hoc test at a significance level of 0.05. RESULTS Setting time Setting times of the investments with different concentrations of a K2SO4 solution are summarized in Table 1. The setting time mixed with the 0%

Setting time TheVicatsneedlepenetrationtestaccordingtoISO9694:199610) was used to measure the setting time; the diameter and load of the Vicats needle were 2 mm and 3 N, respectively. A paraffin wax ring (diameter:50mm;height:20mm)waspreparedona glass plate.  The freshly mixed investment was poured into a wax ring to evaluate the setting time.  Thesettingtimewasrecordedasthetotaltimefrom thestartofmixingtothetimewhentheneedlefailed tomakeadepthofmorethan1mmonthesurfaceof theinvestment.Threerepetitionsweredoneforeach investment. Compressive strength Compressive strengths of the cylindrical specimen, 10  20 mm, were measured at 24 hours after the startofmixing(greenstrength).Thespecimensafter firing up to 700C at a heating rate of 10C/min were maintained for 1 hour, then cooled to room temperature in the furnace, and measured for fired strength.  A universal test machine (Model 1125, Instron, Canton, MA, USA) was used at a crosshead speed of 1 mm/min.  Five repetitions were done for eachinvestment. Setting expansion The freshly mixed investment was put into a steel ring (30 mm in diameter and 40 mm in length) with one fold of a 0.70 mm thick ring liner sheet (New castinglinerNo.2,GC,Tokyo,Japan).Thechangeof height of the investment in a casting ring was monitored by a non-contact eddy-current displacement transducer (KD 4151-3U1, Kaman Instrumentation Corp., Connecticut, USA) until 24 hours from the start of mixing according to a previous study5).  The setting expansion was determined as the final increased height from the minimum height of the investment.  Three measurementswereperformedforeachinvestment. Thermal expansion The dimensional change during heating of the cylindrical specimen, 6 mm in diameter and 12 mm inheight,after24hoursfromthestartofmixingwas recorded with a dilatometer (Thermoplus 8310, Rigaku, Tokyo, Japan) at a heating rate of 10C/min. The dimensional change from the room temperature to 700C was measured as the thermal expansion. Three measurements for each concentration were performed. Crystalline components Crystalline components of experimental investments mixed with a 0% and a 1% K2SO4solutionbeforeand after firing were analyzed with an X-ray diffractometer (XRD; RAD-II A, Rigaku, Tokyo,

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Table1 Evaluatedpropertiesoftheexperimentalinvestment Settingtime minute 152(4) A  48(3) B  44(2) B  35(1) C  34(1) C Greenstrength MPa 5.81(2.07) G 2.22(0.18) H 2.26(0.18) H 2.15(0.23) H 2.45(0.29) H Firedstrength MPa 1.78(0.65) J,K 2.45(0.61) I 2.13(0.41) I,J 1.66(0.33) J,K 1.63(0.24) K Settingexpansion % 0.19(0.01) D 0.20(0.03) D 0.02(0.02) E 0.05(0.04) E 0.02(0.02) E

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K2SO4 % 0 1 2 3 5

Thermalexpansion at 700C % 0.45(0.04) F 0.42(0.05) F 0.38(0.05) F 0.47(0.03) F 0.45(0.06) F mean(SD)

Values with the same superscripted letters were not significantly different (p>0.05).

Fig.1

Setting expansion curves of experimental investmentsmixedwithdifferentratiosofK2SO4.

Fig.2

Typical thermal expansion curves with different ratiosofK2SO4.

K2SO4 solution was more than 2 hours, but that mixed with the 1% K2SO4 solution dramatically reduced to 48 minutes.  The setting time decreased withahigherconcentrationofK2SO4. Compressive strength Compressive strengths are shown in Table 1.  The green strength mixed with 0% of a K2SO4 solution was 5.81 MPa, which was significantly greater than those mixed with any concentration of the K2SO4 solution (p<0.05).  However, the green strengths mixed with any concentration of the K2SO4 solution were not significantly different. After firing at 700C, the experimental investment showed a lower fired strength with respect to its corresponding green strength.  An investment mixed with a 1% K2SO4 solution showed the highest fired strength of 2.45 MPa. Setting expansion Typicalheightchangesoftheinvestmentmixedwith a 0, 1 and 5% K2SO4solutionareillustratedinFigure 1.  The investment height initially decreased and slightly increased when mixed with a 0 and a 1%

Fig.3

X-raydiffractionpatternsoftheinvestmentsmixed with 0% and 1% K2SO4 solutions (before and after firing).

K2SO4 solution; however, when mixed with 2, 3, and 5% K2SO4 solution, the increase of the height was very small after once decreased. The final setting expansions after 24 hours from the start of mixing are summarized in Table 1. The final setting expansions of a 0 and 1% K2SO4 solution were 0.19

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Fig. 4

Mesh type wax pattern (a); Cast specimen with experimental investment of 0% K2SO4 solution (b); Cast specimen with experimental investment of 1% K2SO4solution(c).

Fig.5

Vickers hardness values of cast specimens of experimentalinvestmentsatdifferentdepths.

Castability and Micro Vickers hardness Typical cast specimens obtained from 0% K2SO4 and 1% K2SO4 solutions are shown in Fig. 4.  Castability standard deviations obtained from 0% and 1% K2SO4 solutions were 64.2 12.0% and 81.2 14.2%, respectively. These values were not significantly different. The Micro-Vickers hardness (Hv) at different depthsrangedfrom392.2to175.1.Fig.5showsthat the Hv values decreased with deeper measuring points, but no significant differences were found among the hardness from 200 to 500 m deep measuring points.  Therefore, the reaction layer thickness of castings using this experimental investmentwasconsideredtobelessthan200m. DISCUSSION

and 0.20%, respectively. Thermal expansion Typical dimensional changes during heating of the investments are shown in Figure 2.  Each curve shows a slight contraction at approximately 450C. There was no obvious difference among the curves regardless of K2SO4 concentration.  The thermal expansion at 700C ranged from 0.38 to 0.47%, thermal linear contractions were observed during cooling to room temperature, and the dimensional change at 200C was 0.22 to 0.35 %. No significant difference could be found with respect to changes in K2SO4concentration. Crystalline components X-ray diffraction patterns are shown in Fig. 3.  The peaks of MgO and calcium sulfate dihydrate were detected before firing. After firing, peaks of calcium sulfate dihydrate disappeared and those of calcium sulfate dehydrate appeared.  There was no obvious difference between the patterns from the investment mixed with either a 0% or a 1% K2SO4solution.

In our previous study6), gypsum-bonded magnesia investments required a long time to set. Potassium sulfate is commonly used as an accelerator for gypsum.  Syngenite (K2Ca[SO4]2H2O), the reaction product between gypsum and potassium sulfate, has  been considered to accelerate setting reaction12). However, the existence of syngenite was not obvious according to XRD observation.  The setting time of the experimental investment mixed with a 1% K2SO4 solution improved dramatically.  However, the setting time was not remarkably reduced with a higher concentration of K2SO4. Moreover, fluidity of theexperimentalinvestmentdecreasedwithahigher concentration of K2SO4. Although fluidity of a 1% K2SO4 mixture was not good, it was possible to pour an investment because of its thixotropicity when a vibrator was used.  Therefore, the concentration of K2SO4 was considered to be not more than 1% for the lostwaxcastingmethod. The green strength mixed with a K2SO4 solution decreased, which was similar to that of a previous study9).  The effect of potassium sulfate on setting expansion was suggested to reduce the size of calcium sulfate dihydrate crystals; these small

Dent Mater J 2009; 28(3): 301306 crystals might be responsible for the weak green strength.  Fired strengths ranged from 1.63 to 2.45 MPa. The factors responsible for higher fired strength value of an investment mixed with a 1% K2SO4 solution are not known.  Fired strengths of recent commercial gypsum-bonded investments have been reported to be 0.4 to 1.6 MPa13). The fired strengths of gypsum-bonded magnesia investments mixed with a K2SO4 solution were greater than those of the recent commercial gypsum-bonded investments; however, this was not considered to cause a severe problemfortitaniumcasting. The expansion of the investment during setting and heating are generally required for compensating titaniumcastingshrinkage1,14).Thesettingexpansion of the gypsum-bonded magnesia investment in a previous study was small, and those mixed with a K2SO4 solution were equal or smaller.  A similar decrease in setting expansion of the gypsum-bonded investment was also observed when mixed with a K2SO4 solution9).  A small setting expansion is desirable so that the wax pattern does not deform particularly if a casting ring is used.  Thermal expansion did not change with respect to the K2SO4 solution.  The thermal curves showed slight contractions at around 450C because of the  dehydration of MgO as found in previous research5). The amount of thermal expansion of the gypsumbonded magnesia investment was small; therefore, additivesasthermalexpandingagents,suchasmetal powder, might be necessary to obtain a suitable expansion. However, a recently introduced concept using an enlarged wax pattern manufactured by a CAD/CAM system does not require expansion of the mold materials15).  Good adaptation casting can be obtainedwhenthesetechniquesareengaged. Titanium castings could be obtained using the gypsum-bonded magnesia investments mixed with K2SO4 solutions.  The casting system and wax pattern of the present study were different from our previous report4).  However, the reaction layers of titanium castings were observed as hard surface layers of less than 200 m.  The thickness of this reaction layer was the same or less compared to thosepreviousinvestigations2,16). These results suggest that properties of the gypsum-bonded magnesia investment, particularly thesettingtime,couldbeimprovedwhenmixedwith a K2SO4 solution.  Taking into account the investing behavior, a 1% K2SO4 solution was suitable for casting.Titaniumcastingscouldbeobtainedwiththe gypsum-bonded magnesia investment mixed with a 1% K2SO4solution.However,furtherresearchshould becarriedouttoobtainaccuratetitaniumcastings.

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ACKNOWLEDGMENTS The authors wish to express their sincere thanks to Noritake Dental Supply Co. Ltd., Nagoya, Japan for providing alpha hemi hydrate gypsum for this researchwork. REFERENCES
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