48

Journal of Oral Science, Vol. 62, No. 1, 48-51, 2020

Original article
Effects of composition on the hardness of orthodontic adhesives
Yasuhiro Namura1,2), Toshiki Takamizawa3,4), Yasuki Uchida1,2), Mizuki Inaba1,2), Daichi Noma5), Tomoko Takemoto5),
Masashi Miyazaki3,4), and Mitsuru Motoyoshi1,2)
1)
Department of Orthodontics, Nihon University School of Dentistry, Tokyo, Japan
2)
Division of Clinical Research, Dental Research Center, Nihon University School of Dentistry, Tokyo, Japan
3)
Department of Operative Dentistry, Nihon University School of Dentistry, Tokyo, Japan
4)
Division of Biomaterials Science, Dental Research Center, Nihon University School of Dentistry, Tokyo, Japan
5)
Department of Oral Structural and Functional Biology, Nihon University Graduate School of Dentistry, Tokyo, Japan
(Received January 28, 2019; Accepted April 6, 2019)

Abstract: Although there have been improvements in bracket systems Materials and Methods
precoated with adhesive, removal of adhesive remnants continues to be
problematic. This study compared the hardness and maintainability of pre- Materials
coated adhesive with other commercial adhesives. Knoop hardness values The adhesives used are listed in Table 1. Two adhesives (XT adhesive:
were measured after light- or chemical-induced initial curing, immersion Transbond XT; 3M Unitek, Monrovia, CA, USA and 4-META/MMA-
in distilled water at 37°C for 24 h and 1,000 and 10,000 thermal cycles TBB adhesive: Super-Bond Orthomite; Sun Medical, Moriyama, Japan)
after 24 h. Additionally, the forces required to move brackets by 0.5 mm were used to bond the ceramic brackets (Clarity Advance, 3M Unitek),
were measured during bracket positioning, and brackets bonded to bovine and their hardness was also measured. Additionally, adhesive-precoated
enamel were examined by field-emission scanning electron microscopy. brackets (Precoated adhesive: APC Flash-Free Adhesive-Coated Appli-
The Knoop hardness values of the precoated adhesives were lower than ance; 3M Unitek) were studied. With the brackets being held in position,
those of commercial resin composite adhesives, and hardness was depen- 0.5 µg polyurethane sponges soaked in bonding agent (unfilled adhesive:
dent on the amount of filler in the resin matrix. The ability to maintain the Transbond XT primer; 3M Unitek) were pressed to the base of the brackets
device position may depend on the resin matrix composition. Precoated and bonded (cured) by light from a curing unit.
adhesives with less filler and more matrix material are light curable, and
remnant resin may be easily removed. Knoop hardness
The brackets and adhesives were held with a polyester matrix tape between
Keywords; composite resins, dental bonding, hardness tests the movable tip of a height gauge (HDS-H30C; Mitutoyo, Kawasaki,
Japan) and a metal slab. The adhesive thickness was 100 µm (Fig. 1).
Light-cured adhesives were irradiated for 20 s by a hand-held curing unit
Introduction (Optilux 501; SDS Kerr, Danbury, CT, USA). The brackets were removed
from the height gauge and then re-exposed to light from the curing unit
Orthodontic brackets and adhesives must be removed following treatment. for an additional 20 s (initial curing). The 4-META/MMA-TBB adhesive,
Remnant adhesive on the teeth is removed using carbide bars and pliers; which is chemically cured, was held in place for 10 min until initial curing
however, these instruments may damage the teeth [1]. Dimethacrylate was achieved. Brackets with cured adhesives were immersed in distilled
resin composites are commonly used as orthodontic adhesives, and most water at 37°C for 24 h following initial curing and then subjected to 1,000
can be light cured. However, the removal of any remnant resin is difficult and 10,000 thermal cycles between water baths at 4°C and 60°C (30 s dwell
and time consuming. The remnants exhibit high elastic coefficients and times in each bath). For each specimen in each period (n = 8), the Knoop
high hardness values due to the inclusion of inorganic fillers. Resins of hardness at the center of the adhesive bond to the bracket was measured
the 4-methacryloyloxyethyl trimellitate anhydride/methyl methacrylate- using a microhardness tester (HMV-2; Shimadzu, Kyoto, Japan) after
tri-n-butylborane (4-META/MMA-TBB) type (with no inorganic filler) application of a 245.2 mN load for 15 s. Mean values were then calculated.
have been widely adopted in Japan [2], not only as orthodontic adhesives
[3,4] but also as a luting material for resin-bonded fixed partial dentures Bracket mobility
[5-8]. These resins are easy to remove because of the lack of filler but are Bovine tooth crowns were embedded in self-curing acrylic resin (Tray
inconvenient to handle due to the chemical curing required. Resin; Shofu, Kyoto, Japan) and adjusted so that the bracket-bearing
Adhesive-precoated brackets have been used widely in clinical surface lay parallel to the blade tip of a universal testing machine (5567;
orthodontics [9] as the tooth-bonding time is short [10]. Recently, sys- Instron, Norwood, MA, USA). The enamel surfaces were flattened and
tems precoated with “flash-free” adhesives have become available. The polished with waterproof silicon-carbide paper (#400, #600) to ensure that
adhesive resin matrix is maintained on non-woven polypropylene on the the experimental conditions remained constant. Immediately following the
bracket base. In addition, adhesive overflow is greatly reduced. Inorganic placement of adhesive on the bracket base, or immediately following the
fillers are contained not only in conventional resin composite adhesives but removal of a self-adhesive device from its package, the bracket was placed,
also in precoated adhesives. However, the degree of hardness of precoated in contact with the blade tip, onto a tooth surface treated according to the
adhesive cured under brackets has not been determined. This study com- manufacturer’s instructions (Fig. 2). The maximum force required to move
pared precoated adhesive with adhesives of differing composition relative the adhered bracket by 0.5 mm at a crosshead speed of 1 mm/min with a 1
to the degree of adhesive hardness and the ease of maintaining bracket kN load cell was measured. All measurements were performed at 23 ± 1°C
position during the positioning process. The null hypothesis was that the and relative humidity of 50 ± 5%.
degree of hardness of the precoated adhesive and the ability to maintain
bracket position would not differ from adhesives with varying proportions Scanning electron microscopy
of adhesive and filler. Ceramic brackets bonded to bovine enamel surfaces were examined using
field-emission scanning electron microscopy (SEM; ERA-8800FE, Elionix
Ltd., Tokyo, Japan). Each enamel surface was treated as recommended in
Correspondence to Dr. Yasuhiro Namura, Department of Orthodontics, Nihon University School of
Dentistry, 1-8-13 Kanda-Surugadai, Chiyoda-ku, Tokyo 101-8310, Japan the manufacturer’s instructions. Next, ceramic brackets were bonded onto
Fax: +81-3-3219-8105 E-mail: [email protected] the enamel surfaces. Following immersion in distilled water for 24 h at
doi.org/10.2334/josnusd.19-0035 37°C, the bonded specimens were embedded in an epoxy resin (Epon 812;
DN/JST.JSTAGE/josnusd/19-0035 Nisshin EM, Tokyo, Japan) and sectioned longitudinally with a diamond
 49

Table 1   Adhesive composition

Adhesive/trade name, manufacture Composition (wt%)

Unfilled/Transbond XT light cure adhesive primer, 3M Unitek, Monrovia, CA, USA
[2-hydroxy-3-[4-[2-[4-[2-hydroxy-3-(2-methylprop-2-enoyloxy)propoxy]phenyl]propan- 45-55
2-yl]phenoxy]propyl] 2-methylprop-2-enoate
2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate 45-55
triphenylstibane <1
2-(4-(dimethylamino)phenyl)ethanol <0.5
d,l-camphorquinone <0.3
hydroquinone <0.03
Precoated/APC Flash Free Adhesive Coated Appliance, 3M Unitek
2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 30-45
2-methylprop-2-enoate
[2-hydroxy-3-[4-[2-[4-[2-hydroxy-3-(2-methylprop-2-enoyloxy)propoxy]phenyl]propan- 30-45
2-yl]phenoxy]propyl] 2-methylprop-2-enoate
polypropylene 10-20
silane treated ceramic 5-15
4-META/MMA-TBB/Super-Bond Orthomite, Sun Medical, Moriyama, Japan
Super-Bond Catalyst V:
partially oxidized tri-n-butylborane (TBB) 60-95
n-hexane 5-40
Super-Bond C&B Quick Monomer:
methyl methacrylate (MMA) 70-99
2-(2-methylprop-2-enoyloxy)ethyl 1,3-dioxo-2-benzofuran-5-carboxylate (4-META) 3-20
Super-Bond Polymer brush-dip F3:
poly(methyl methacrylate) (PMMA) balance
sodium fluoride <10
Super-Bond teeth primer:
4-META 10-30
sodium sulfite 1-5
acetone 20-40
water 40-80
XT/Transbond XT light cure adhesive, 3M Unitek
Transbond XT Adhesive in Syringes:
dioxosilane;3-trimethoxysilylpropyl 2-methylprop-2-enoate 70-80
[2-hydroxy-3-[4-[2-[4-[2-hydroxy-3-(2-methylprop-2-enoyloxy)propoxy]phenyl]propan- 10-20
2-yl]phenoxy]propyl] 2-methylprop-2-enoate
2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 5-10
2-methylprop-2-enoate
dioxosilane <2
diphenyliodanium;hexafluorophosphate <0.2
Etching gel:
water 55-65
phosphoric acid 30-40
amorphous silica 5-10
Obtained from safety data sheet for each material

Fig. 1   Schematic image of specimen preparation for the Knoop hardness test. Specimens Fig. 2   Force required to maintain position. The force applied prior to perpendicular move-
were held between the movable tip of a height gauge and a metal slab (adhesive thickness ment was measured.
was 100 µm), followed by curing.

saw (Isomet Low-Speed Saw; Buehler, Lake Bluff, IL, USA). The sec- kV, ion current density 0.4 mA/cm2) perpendicular to the polished surfaces.
tioned surfaces were polished to a high gloss with abrasive discs (Fuji Star Finally, all specimens were coated with a thin film of gold in a vacuum
Type DDC; Sankyo Rikagaku Co. Ltd., Okegawa, Japan), followed by evaporator (Quick Coater Type SC-701; Sanyu Denchi Inc., Tokyo, Japan)
diamond paste (DP-Paste; Struers, Ballerup, Denmark) to a particle size and examined using an operating voltage of 10 kV.
of 0.25 μm. All specimens were dehydrated in a series of tert-butyl alcohol
baths (50% [v/v] for 20 min, 75% for 20 min, 95% for 20 min, and 100% Statistical analysis
for 2 h) and then transferred to a critical-point dryer (Model ID-3; Elionix Descriptive statistics, including means and standard deviations were
Ltd., Tokyo, Japan) for 30 min. They were then subjected to argon-ion calculated for each group using SPSS software (SPSS Inc., Chicago, IL,
beam etching (EIS-200ER; Elionix Ltd.) for 40 s (acceleration voltage 1.0 USA). The Kolmogorov-Smirnov and Levene tests were used to verify
50

Table 2   Knoop hardness values (HK) by time

Time point
Adhesive
Initial curing 24 h after initial curing 1,000 thermal cycles after 24 h 10,000 thermal cycles after 24 h
Unfilled 3.0 (0.5)e 5.2 (0.5)a 8.2 (1.6)b, c, f 5.9 (1.1)a, f
Precoated 5.2 (0.4) a
6.8 (1.1) a, b
10.8 (1.0) c, j
10.0 (0.6)c, d, j
4-META/MMA-TBB 8.5 (1.2)b, d, i 13.0 (3.2)c, i, j 13.9 (2.6)j 9.4 (1.1)c, i, j
XT 25.6 (1.5)g 27.6 (4.2)g 36.3 (2.9)h 40.8 (5.1)h
Values are given as mean (SD) all in HK.
Superscript letters indicate significant differences (P < 0.05) between different letters, determined by the Games-Howell test.

Table 3   Force (N) required to maintain position of the adhesives

Adhesive Mean force

Unfilled† -
Precoated 0.54 (0.66)a
4-META/MMA-TBB 0.94 (1.03)a, b
XT 1.21 (0.48)b
Values are given as mean (SD) all in N.
Superscript letters indicate significant difference (P < 0.05) between different letters, deter-
mined by the Scheffé test.
†
For unfilled adhesive, maintenance force could not be measured because the adhesive was
cured while holding the bracket with dental tweezers.

the normality and homogeneity of variance. Differences in Knoop hard-

ness values between groups were evaluated using the Games-Howell test,
followed by two-way analysis of variance (ANOVA). To evaluate bracket Fig. 3   Typical curves of force required to maintain position for each adhesive. The curves
mobility, the Scheffé test, followed by one-way ANOVA, was used to peak at the initiation of displacement.
compare adhesives. P-values <0.05 were considered to be statistically
significant.

Results (Fig. 4b). For the precoated adhesive, irregularly sized filler particles were
observed in the adhesive layers (Fig. 4d). With the 4-META/MMA-TBB
Knoop hardness adhesive, poly(methyl methacrylate) resin particles, 10-50 μm in diameter,
Knoop hardness values (HK) of all adhesives are listed in Table 2. Two-way were observed in the adhesive layers (Fig. 4f). For the XT adhesive, some
ANOVA was not performed because the Levene test revealed no homo- plucking of irregularly shaped fillers was evident (Fig. 4h).
geneity of variance even though the Kolmogorov-Smirnov test revealed
normality. Multiple comparisons were performed among all groups. In Discussion
all tests, the Knoop hardness values of the XT adhesive were highest,
whereas those of the unfilled adhesive were lowest. For the precoated and Significant differences in Knoop hardness and bracket position stability
XT adhesives, the hardness values at 1,000 and 10,000 thermal cycles of the tested adhesives were noted in this study. The null hypothesis was
were significantly higher than at initial curing and 24 h following initial rejected as the grinding and immobilizing capacities of the adhesives dif-
curing. The hardness values of the unfilled resin and 4-META/MMA-TBB fered. The Knoop hardness differed not only among adhesives but also
adhesives peaked at 1,000 thermal cycles and decreased at 10,000 thermal among time periods. Freeman et al. used 1,000 thermal cycles during testing
cycles to values similar to those at initial curing. For all of the adhesives, [11], more than the ISO standard of 500 cycles [12]. Approximately 10,000
there was no significant difference between hardness at 1,000 and 10,000 cycles correspond to 1 year of clinical use [13,14]. Wattanawongpitak et
thermal cycles. al. examined the effect of thermal stress (0; 500; and 5,000 cycles) on resin
composites, finding that marginal and cavity gap numbers depended on the
Maintenance forces and bracket displacement number of cycles [15]. Jurubeba et al. reported that the bond strength of
Maintenance forces (N) and bracket displacement are noted in Table 3 and orthodontic adhesives was affected after >7,000 thermal cycles [16]. In this
Fig. 3. Maximum forces were attained at the initiation of force loading for study, Knoop hardness values did not change between 1,000 and 10,000
all adhesives (Fig. 3). One-way ANOVA, based on the results in which the cycles. Therefore, grinding properties may not change over the course
Levene and Kolmogorov-Smirnov tests revealed homogeneity of variance of several days to 1 year following treatment. Amato et al. recorded the
and normality, were statistically significant. The forces for precoated adhe- Knoop hardness values of 1 mm thick samples of orthodontic adhesives,
sives were significantly lower than those for the XT adhesive. When the including Transbond XT, with the hardness of Transbond XT averaging 30
4-META/MMA-TBB adhesive is brushed on, the powder/liquid mixture is HK [17]. The values in this study for Transbond XT were similar, 25.6-
heterogeneous; therefore, the force required to maintain bracket position 40.8 HK, although the specimen size differed.
was rather wide. The force required to maintain the position of the unfilled The proportion of filler affects the hardness of resin composites [18].
adhesive could not be measured because the adhesive was cured while Of the adhesives in this study, the filler proportion was greatest in the
holding the bracket with dental tweezers. XT adhesive (70-80%) and lowest in the precoated adhesive (5-15%).
The Knoop hardness of the precoated adhesive was approximately 4-fold
SEM findings that of the XT adhesive, indicating that hardness depends on the relative
Representative SEM images of ceramic brackets bonded to bovine enamel proportions of filler and resin. The hardness of the precoated adhesive
are shown in Fig. 4. All tested materials exhibited excellent adaptation was 1.32-1.74-fold that of the unfilled adhesive and 0.52-1.06-fold that of
between the enamel and adhesive. Although all adhesive layers were of 4-META/MMA-TBB, indicating the hardness of the precoated adhesive
similar thickness (approximately 100-200 μm; Fig. 4a, c, e, g), their appear- was similar to or less than that of 4-META/MMA-TBB.
ance was material dependent. A homogenous adhesive layer that appeared On SEM of the unfilled adhesive, filler was absent from the methacry-
to be composed of dimethacrylate was observed for the unfilled adhesive late matrix resin supported by the polyurethane sponge ([a] scaffold; Fig.
(Fig. 4a). Additionally, gaps formed by the urethane sponges were apparent 4b). In the precoated adhesive, filler was sparsely scattered throughout
 51

depend on the matrix resin proportion but not that of the filler. As the
precoated adhesive specimens were too small to allow viscosity assess-
ment, the ability to maintain position of the thin specimens was measured.
The mean force required to maintain position of the precoated adhesive
was approximately 0.5 N, significantly lower than that of the XT adhesive.
Additionally, as the unfilled adhesive could not maintain bracket position
until after being cured, the force required to maintain position could not be
studied. Precoated adhesives are more readily removed, and the low-level
Knoop hardness facilitates their placement onto brackets and convenient
bracket positioning.

Acknowledgments
This work was supported, in part, by the Sato Fund, Nihon University
School of Dentistry, in 2017.

Conflict of interest
The authors declare that there is no conflict of interest regarding the pub-
lication of this article.

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