polymers

Article
Assessment of Degree of Conversion and Volumetric Shrinkage
of Novel Self-Adhesive Cement
Long Ling *, Yulin Chen and Raj Malyala

Glidewell Dental, Irvine, CA 92612, USA; [email protected] (Y.C.); [email protected] (R.M.)

* Correspondence: [email protected] or [email protected]

Abstract: The degree of monomer conversion and polymerization shrinkage are two of the main
reasons for potential adhesion failure between the tooth structure and the restoration substrate. To
evaluate the degree of conversion and polymerization shrinkage of a newly developed self-adhesive
resin cement, the degree of conversion (DC) was measured using FTIR under different activation
modes, temperatures, and times. Volumetric shrinkage was tested using the AcuVol video imaging
method. The experimental cement showed a higher DC than other cements under self-curing. The
DC of the experimental cement was higher than that of other cements, except SpeedCem Plus under
light curing. The experimental cement had a higher DC than other cements, except SpeedCem Plus in
some conditions under dual curing. All self-adhesive cements had a higher DC at 37 ◦ C than at 23 ◦ C
under self-curing, and there was no statistical difference between 23 ◦ C and 37 ◦ C under light curing.
All self-adhesive cements showed a significantly higher DC at 10 min than at 5 min under self-curing.
There was no statistical difference between 5 min and 10 min for most cements under dual curing.
All self-adhesive cements statistically had the same volumetric shrinkage under light curing and
self-curing. The newly developed self-adhesive resin cement exhibited a higher degree of conversion
and similar volumetric shrinkage compared to these commercial self-adhesive resin cements.

Keywords: self-adhesive resin cements; degree of conversion; shrinkage

1. Introduction
Citation: Ling, L.; Chen, Y.; Malyala,
R. Assessment of Degree of
Self-adhesive resin cement (SARC) has gained great attention, and it has been increas-
Conversion and Volumetric Shrinkage
ingly applied since RelyX Unicem (3M ESPE) first launched in the market [1]. Compared
of Novel Self-Adhesive Cement.
to conventional resin cements (total-etch/esthetic and self-etch/adhesive resin cements),
Polymers 2024, 16, 581. https:// self-adhesive resin cement has simplified the cementation technique and process by intro-
doi.org/10.3390/polym16050581 ducing acidic monomers without separate etching or priming, resulting in lower technique
sensitivity and postoperative sensitivity [1–3]. Like conventional resin cements, however,
Academic Editor: Sufyan Garoushi
some factors may cause poor adhesion between the tooth structure and the restoration
Received: 18 January 2024 substrate, resulting in inferior clinical performance [4,5].
Revised: 10 February 2024 Two of the main reasons for such potential adhesion failure are the degree of monomer
Accepted: 17 February 2024 conversion (DC) and polymerization shrinkage [4,6–10]. When the monomers are poly-
Published: 21 February 2024 merized, the degree of conversion represents what percentage of monomers are converted
into polymers, indicating the polymerization ability or curing efficiency of resin monomers.
The degree of conversion has a great influence on physical properties, like water sorption
and solubility [11], mechanical properties, such as hardness, fracture toughness, and wear
Copyright: © 2024 by the authors.
resistance [12–14], and adhesive properties [6,7,10], as well as biocompatibility [15,16].
Licensee MDPI, Basel, Switzerland.
Polymerization shrinkage happens with the decreased free volume due to the change of
This article is an open access article
intermolecular forces like van der Waals into covalent bond when monomer molecules
distributed under the terms and
were converted to polymers. Shrinkage is widely recognized as an inherent phenomenon of
conditions of the Creative Commons
polymerizable monomers, which is the clinician’s primary concern when placing resin com-
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
posite restorations [17,18]. When polymerization occurs, polymerization shrinkage produces
4.0/).
the contraction stress, and it can affect the marginal integrity and form defects at the bonding

Polymers 2024, 16, 581. https://doi.org/10.3390/polym16050581 https://www.mdpi.com/journal/polymers

Polymers 2024, 16, 581 2 of 15

interface, resulting in marginal leakage and eventually bonding failure [17–20]. Therefore,
self-adhesive resin cement with a higher degree of conversion and lower polymerization
shrinkage is always highly desirable.
Recently, we reported a novel self-adhesive resin cement (SARC) with favorable
physical, mechanical, and adhesive properties and evaluated its working time and setting
time, consistency, film thickness, water sorption and solubility, flexural strength and
modulus, and bond strength [21]. This study aims to investigate the degree of conversion
and volumetric shrinkage of the newly developed self-adhesive resin cement and compare
it with other commercial self-adhesive resin cements. The hypothesis is that this new
self-adhesive resin cement has a higher degree of conversion, especially for self-curing, and
similar volumetric shrinkage compared to other commercial self-adhesive resin cements.

2. Materials and Methods

2.1. Study Design
In this in vitro study, a newly developed self-adhesive resin cement, as an experimental
cement, and five commercially available self-adhesive resin cements, as control materials,
were examined to compare the degree of conversion (DC) and volumetric shrinkage. The
degree of conversion was studied in detail at different activation modes (self-cure (SC), light
cure (LC), and dual cure (DC)), temperatures (23 ◦ C and 37 ◦ C), and times (5 min and 10 min
for self-cure, 20 s for light cure) based on a comprehensive consideration of ISO 4049 [22], a
clinic cementation protocol, and the work and set times of most resin cements [21,23–27].
Therefore, 12 curing scenarios were set up, as shown in Table 1. Volumetric shrinkage
was collected for self-cure at 60 min and for light cure at 5 min. All testing materials and
methods are described in detail below.

Table 1. Curing scenarios of self-adhesive resin cements used in this study.

Curing
Self-Cure (SC) Light Cure (LC) Dual Cure (DC)
Scenarios
1 5 min at 23 ◦ C
2 5 min at 37 ◦ C
3 10 min at 23 ◦ C
4 10 min at 37 ◦ C
5 20 s at 23 ◦ C
6 20 s at 37 ◦ C
7 SC 10 min + LC 20 s at 23 ◦ C
8 SC 10 min + LC 20 s at 37 ◦ C
9 LC 20 s + SC 10 min at 23 ◦ C
10 LC 20 s + SC 10 min at 37 ◦ C
11 LC 20 s + SC 5 min at 23 ◦ C
12 LC 20 s + SC 5 min at 37 ◦ C

2.2. Materials
Experimental self-adhesive resin cement (Experimental SARC or Experimental) was
formulated using our proprietary adhesive resin and filler technology, which included
acidic monomer, non-acidic monomers, dual-cured initiator systems, inhibitor, and fillers.
10-methacryloxydecyl dihydrogen phosphate (10-MDP) as an acidic monomer, bisphenol A
diglycidyl ether dimethacrylate (BisGMA) as rigid space-filling monomers, and other dental
monomers, such as urethane dimethacrylate, were used for the resin system. Dual-curing
initiator systems were composed of cumene hydroperoxide/(2,3-difluorophenyl)thiourea as a
redox initiator system for self-curing and camphorquinone (CQ), bis(2,4,6-trimethylbenzoyl)-
phenyl-phosphineoxide, and ethyl 4-dimethylaminobenzoate as photo-initiators for light
curing. 2,6-di-(tert-butyl)-4-methylphenol was used as an inhibitor. Fillers consisted of
barium boron fluoroaluminosilicate glass, OX-50 fumed silica, and ytterbium fluoride.
The homogeneous resin mixtures were first obtained by stirring resin monomers with the
additives until dissolved. The resulting resin mixtures were further mixed with fillers until
Polymers 2024, 16, 581 3 of 15

a uniform, flowable paste was formed. Five commercially available self-adhesive resin
cements, including Maxcem Elite (Kerr, Orange, CA, USA), RelyX Unicem 2 (3M ESPE, St.
Paul, MN, USA), SpeedCem Plus (Ivoclar Vivadent, Schaan, Liechtenstein), SmartCEM 2
(Dentsply Sirona, York, PA, USA), and Calibra Universal (Dentsply Sirona, York, PA, USA),
major self-adhesive resin cements with some similar resins, fillers, and filler loading in
the market, were selected in this study for comparison. Further information about the
self-adhesive resin cements used in this study is shown in Table 2.

Table 2. Self-adhesive resin cements used in this study.

Filler Content
Material Manufacturer Resin Filler
(wt.%)
Barium boron
BisGMA, UDMA, TEGDMA, fluoroaluminosilicate
Exp. SARC Glidewell 70
MDP, initiators and inhibitor glass, fumed silica,
ytterbium fluoride
Methacrylate esters, GPDM, Mineral fillers,
MaxCem Elite Kerr 69
HEMA, activators and stabilizers ytterbium fluoride
Methacrylated phosphoric esters,
dimethacrylates, TEGDMA,
Glass fillers, silica,
RelyX Unicem 2 3M ESPE acetate, sodium persulfate, 70
calcium hydroxide
substituted pyrimidine,
stabilizers
UDMA, TEGDMA, PEGDMA,
Barium glass, silica 75 (Base)
SpeedCEM Plus Ivoclar Vivadent DDDMA, MDP, dibenzoyl
ytterbium trifluoride /69.8 (Cat)
peroxide, stabilizer
UDMA, EBPADMA, Di- and Barium boron
tri-functional function diluents, fluoroaluminosilicate
SmartCEM 2 Dentsply Sirona 69
PENTA, 4-META, initiators, glass, amorphous
accelerators, stabilizer silicon dioxide
UDMA, Di- and Barium boron fluo
Tri-Methacrylate, Phosphoric roaluminosilicate,
Calibra Universal Dentsply Sirona 73
acid modified acrylate, initiators, amorphous silicon
accelerators, stabilizer, BHT dioxide
BisGMA—Bisphenol A diglycidyl ether dimethacrylate; UDMA—Urethane dimethacrylate; TEGDMA—
Triethyleneglycol dimethacrylate; MDP—Methacryloyloxydecyl dihydrogenphosphate; GPDM—Glycerol phos-
phate dimethacrylate; HEMA-2—Hydroxyethyl methacrylate; PEGDMA—Polyethylene glycol dimethacrylate;
DDDMA-1,10—decandiol dimethacrylate; EBPADMA—Ethoxylated Bis Phenol A Dimethacrylate; PENTA—
Dipentaerythritol penta-acrylate monophosphate; 4-META-4—Methacryloxyethyl trimellitate anhydride; CQ—
camphorquinone; EDMAB—ethyl 4-dimethylaminobenzoate; BHT—Butylated hydroxytoluene. The compositions
of the resin and filler were obtained from the manufacturers.

2.3. Degree of Conversion (DC)

The degree of conversion was measured using a Bruker ALPHA FTIR spectrometer
with a Diamond Crystal ATR (Bruker, Billerica, MA, USA). Disk specimens (10 mm diameter
× 1 mm thick, n = 5) were placed directly on the diamond crystal plate and cured in situ
at different activation modes (self-cure, light cure, and dual cure), temperatures (23 ◦ C
and 37 ◦ C), and times (5 min and 10 min for self-cure, 20 s for light cure). All spectra
were recorded for uncured and cured cements at a wavelength range of 4000–400 cm−1 , a
resolution of 4 cm−1 , and a sample scan time of 24 s. The DC was calculated with the peak
heights of aliphatic double bond absorption around 1638 cm−1 and of the aromatic double
bond around 1607 cm−1 as the internal standard (for most cements; otherwise, the carbonyl
group around 1710 cm−1 for cement without absorption around 1607 cm−1 was used).

DC (%) = [1 − (Ap /Ap0 )/(Am /Am0 )] × 100

Polymers 2024, 16, 581 4 of 15

where Ap is the peak height of the cured cement (polymer) and Am is the peak height
of uncured cement (monomer) at 1638 cm−1 and Am0 and Ap0 are the peak heights at
1607 cm−1 (or 1710 cm−1 ) before and after curing, respectively.

2.4. Volumetric Shrinkage

Volumetric shrinkage (%) was measured using an AcuVol 2 device (Bisco, Inc. Schaum-
burg, IL, USA). Bubble-free, semispherical specimens of resin materials were manually
formed by carefully placing the specimen (approximately 20 mg) onto the base of the
sample holder. The curing gun was placed approximately 2 mm from the specimen and
light cured for 20 s with a light intensity of approximately 1000 mW/cm2 (Bluephase
Style, Ivoclar Vivadent AG, Schaan, Liechtenstein). The volumetric shrinkage of each resin
material (n = 5) was obtained at 5 min for light curing and at 60 min for self-curing to ensure
that the volumetric shrinkage became constant at 5 min for light curing and at 60 min for
self-curing.

2.5. Flexural Strength, Flexural Modulus, Water Sorption, and Solubility

Flexural strength, flexural modulus, water sorption, and solubility were determined
in accordance with ISO-4049 (2009) in our previous study [21].

2.6. Statistical Analysis

Statistical analysis was performed using Minitab 18 Statistical Software (Minitab,
LLC, State College, PA, USA). The results for the degree of conversion and volumetric
shrinkage were analyzed through one-way ANOVA and Tukey’s post hoc comparison. The
significance level was set at α = 0.05. The Pearson correlations were analyzed according
to the simple linear regression between the degree of conversion and flexural strength,
flexural modulus, and water solubility.

3. Results
The test results for the degree of conversion and volumetric shrinkage of experimental
and commercially available self-adhesive resin cements, which include the effects of activa-
tion modes, temperature, and time, and the correlations between DC and flexural strength,
modulus, and water solubility, respectively, are shown in Figures 1–10.

3.1. Effect of Cement Materials on DC under Different Activation Modes

Under self-curing for 5 min and 10 min at 23 ◦ C and 37 ◦ C (Table 1, curing scenar-
ios 1–4), the Experimental SARC showed a significantly higher DC than other cements
(p < 0.001); however, statistically, it was the same as Maxcem Elite and SpeedCem Plus for
10 min at 37 ◦ C (p > 0.05) (Figure 1).
Under light curing for 20 s at 23 ◦ C and 37 ◦ C (Table 1, curing scenarios 5 and 6), the
DC of the Experimental SARC was statistically the same as that of Maxcem Elite, RelyX
Unicem 2, and SpeedCem Plus at 23 ◦ C and SpeedCem Plus at both 23 ◦ C and 37 ◦ C
(p > 0.05). It was significantly higher than SmartCEM 2 and Calibra Universal at 23 ◦ C and
Maxcem Elite, RelyX Unicem 2, SmartCEM 2, and Calibra Universal at 37 ◦ C (p < 0.001)
(Figure 2).
Polymers 2024, 16,
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70
70

A4
A4
60 A4
A4
60 A3
A2 A3 A4
(%)

A2 A4
50
(%)

50 A1
conversion

B3 B4
A1 A2,B2
conversion

B2 B3 B4
A2,B2 B3,C3
B2 B2 B4
40 B3,C3
B2 B4
40 C3,D3 D3
C3,D3 D3
ofof

30 C2
30 C4 B1 B1,C1 C2
Degree

B1
C4 B1 B1 B1,C1
Degree

B1
B1
C2
20 C2 E3
20 E3

10
10 C1
C1

0
0 Exp Maxcem Elite RelyX Unicem 2 SpeedCem Plus SmartCEM 2 Calibra Universal
Exp Maxcem Elite RelyX Unicem 2 SpeedCem Plus SmartCEM 2 Calibra Universal
5min,23°C 43.2 24.6 5.6 22.5 24.5 20.5
5min,23°C 43.2 24.6 5.6 22.5 24.5 20.5
5min,37°C 49.1 41.1 17.5 38.5 36.6 23.4
5min,37°C 49.1 41.1 17.5 38.5 36.6 23.4
10min,23°C 53.2 39.4 16.6 40.9 34.4 32.1
10min,23°C 53.2 39.4 16.6 40.9 34.4 32.1
10min,37°C 57.6 51.0 24.0 56.1 43.3 36.8
10min,37°C 57.6 51.0 24.0 56.1 43.3 36.8
Self-adhesive resin cements
Self-adhesive resin cements

Figure 1. Degree of conversion of self-adhesive resin cements for self-curing (5 min and 10 min at
Degree of
Figure 1. Degree
Figure of conversion
conversion of
of self-adhesive
self-adhesive resin
resin cements
cements for
for self-curing
self-curing (5
(5 min
min and
and 10
10 min at
23 ◦°C and 37 ◦°C). (Value bars with the same letter are statistically equivalent between the tested
23 °CC and
and 37 °C).
C). (Value
(Value bars with the same letter are statistically equivalent between the tested
groups).
groups).

60
60
A1
A1 A2
A2
A1 A2
A2 A1
50 A1 A2,B2
A1 A1
50 B2 A2,B2
A1 B2
(%)
(%)

40 B1 C2
conversion

40 B1 C2 C2
B1
conversion

B1 C2

30
30
Degreeofof

20
Degree

20

10
10

0
0 Exp Maxcem Elite RelyX Unicem 2 SpeedCem Plus SmartCEM 2 Calibra Universal
Exp Maxcem Elite RelyX Unicem 2 SpeedCem Plus SmartCEM 2 Calibra Universal
23°C 49.7 44.2 46.3 51.1 35.1 34.4
23°C 49.7 44.2 46.3 51.1 35.1 34.4
37°C 50.0 43.4 46.2 51.3 37.0 34.1
37°C 50.0 43.4 46.2 51.3 37.0 34.1

Self-adheisve resin cements

Self-adheisve resin cements

Figure 2. Degree of conversion of self-adhesive resin cements for light curing (20 s at 23 °C and 37
Figure
Figure 2.
2. Degree
Degree ofofconversion
conversion ofofself-adhesive
self-adhesive resin cements
resin forfor
cements light curing
light (20(20
curing s ats 23 °C ◦and
at 23 37
C and
°C). (Value bars with the same letter are statistically equivalent between the tested groups).
°C).◦ (Value bars with the same letter are statistically equivalent between the tested groups).
37 C). (Value bars with the same letter are statistically equivalent between the tested groups).
Polymers 2024, 16,
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15

70
70
A2 A2
A2 A1 A2
A1 A1
60 A1 A2
60 A2
A1,B1 B2
A1,B1
(%)

B2 B2 B2
50
conversioin(%)

B2 B1,C1 B2 B1,C1
50 B1,C1
B1,C1
Degreeofofconversioin

C1
40 C1
40

30
30
Degree

20
20

10
10

0
0 Exp Maxcem Elite RelyX Unicem 2 SpeedCem Plus SmartCEM 2 Calibra Universal
Exp Maxcem Elite RelyX Unicem 2 SpeedCem Plus SmartCEM 2 Calibra Universal
23°C 56.9 50.3 38.7 57.3 44.4 43.9
23°C 56.9 50.3 38.7 57.3 44.4 43.9
37°C 60.9 56.2 46.1 60.1 47.4 49.5
37°C 60.9 56.2 46.1 60.1 47.4 49.5
Self-adhesive resin cements
Self-adhesive resin cements

Figure 3. Degree of conversion of self-adhesive resin

Figure resin cements
cements for
for dual
dual curing
curing (self-curing
(self-curing for
for 10
10 min
min
Figure 3.
3. Degree of conversion of self-adhesive
plus light curing for 20 s at 23 °C ◦and 37 °C).◦(Value bars with the same letter are statistically equiv-
plus light
light curing
curingfor
for2020s at
s at
23 23 C and
°C and 37 (Value
37 °C). C). (Value
bars bars
with with the same
the same letter
letter are are statistically
statistically equiv-
alent between the tested groups).
alent between
equivalent the tested
between groups).
the tested groups).

80
80

A4
70 A4 A4
70 A2 A4 A3
A2 A3 A3
A3 A4,B4 A1 A2
A1 A2
60 A1 A3 A4,B4 A3
B4
60 A1 A1 B2 A3 A3
A1 B2 A1,B1 B2,C2 B4
A1,B1 B2,C2 B3 C4
C4
(%)

B3 C2,D2 B3 C4
50 B1 D2 C4
conversion(%)

B1 C2,D2 B3
50 D2 B1
B1
Degreeofofconversion

40
40

30
30
Degree

20
20

10
10

0
0 Exp Maxcem Elite RelyX Unicem 2 SpeedCem Plus SmartCEM 2 Calibra Universal
Exp Maxcem Elite RelyX Unicem 2 SpeedCem Plus SmartCEM 2 Calibra Universal
LC 20s+SC 5min, 23°C 57.2 54.3 53.0 57.9 46.2 44.3
LC 20s+SC 5min, 23°C 57.2 54.3 53.0 57.9 46.2 44.3
LC 20s+SC 5min, 37°C 63.0 54.5 54.1 57.3 46.5 47.1
LC 20s+SC 5min, 37°C 63.0 54.5 54.1 57.3 46.5 47.1
LC 20s+SC 10min, 23°C 60.9 56.8 54.7 60.3 48.6 47.6
LC 20s+SC 10min, 23°C 60.9 56.8 54.7 60.3 48.6 47.6
LC 20s+SC 10min, 37°C 65.3 58.6 56.5 65.7 48.8 50.5
LC 20s+SC 10min, 37°C 65.3 58.6 56.5 65.7 48.8 50.5
Self-adhesive resin cements
Self-adhesive resin cements
Figure 4. Degree of conversion of self-adhesive resin cements for dual curing (light curing for 20 s
Figure 4. Degree of conversion of self-adhesive resin cements for dual curing (light curing for 20 s
Figure 4. Degreefor
plus self-curing of 5conversion
min and 10ofmin
self-adhesive
at 23 °C andresin cements
37 °C). forbars
(Value dual curing
with (lightletter
the same curingarefor 20 s
statis-
plus self-curing for 5 min and 10 min at 23 °C and 37 °C). (Value bars with the same letter are statis-
ticallyself-curing
plus equivalentfor
between
5 min the
andtested
10 min at 23 ◦ C and 37 ◦ C). (Value bars with the same letter are
groups).
tically equivalent between the tested groups).
statistically equivalent between the tested groups).
x FOR PEER REVIEW 7 of 15
Polymers 2024, 16, 581 7 of 15

100

90
Flexural strength (MPa)

80 R² = 0.5784

70

60

50

40

30

20
20 25 30 35 40 45 50 55 60
Degree of conversion of self-cure (%)

Figure 5. Correlation of 5.degree

Figure of conversion
Correlation of degree ofand flexural
conversion andstrength.
flexural strength.

7
Flexural modulus (GPa)

R² = 0.441
5

3
20 25 30 35 40 45 50 55 60
Degree of conversion of self-cure (%)

Figure 6. Correlation of 6.degree

Figure of conversion
Correlation of degree ofand flexural
conversion andmodulus.
flexural modulus.
 x FOR PEER REVIEW 8 of 15
Polymers 2024, 16, 581 8 of 15

14 PEER REVIEW
Polymers 2024, 16, x FOR 8 of 15

12
14
Water solubility (µg/mm3)

10
12
8 Water solubility (µg/mm3)
10
6 R² = 0.7273
8

4 6 R² = 0.7273

2 4

2
0
30 035 40 45 50 55
-2 30 35 40 45 50 55
-2
Degree of conversion (%)
Degree of conversion (%)

Figure 7. Correlation of 7.
Figure degree of conversion
Correlation ofand
of degree of waterand
conversion
conversion solubility.
and water solubility.
water solubility.

8
8

7 A3 A3 A3
7 A3 A3
A3
A3 A3 A3
A3
A3
6
A3
Volumetric shrinkage (%)

6 A1 A1 A1
A1
A1
5 A1
A1 A1
A1
A1 A2
A1
5 A1 A2 A2 A2 A2
A2
4
A2
A2 A2 A2
A2 A2
4 3

2
3

1
2

0
Exp Maxcem Elite RelyX Unicem 2 SpeedCem Plus SmartCEM 2 Calibra Universal
1 Light-curing (5 min) 4.67 4.71 4.79 5.08 5.06 5.09
Self-curing (5 min) 3.38 3.07 3.24 3.69 3.40 3.39
Self-curing (60 min) 5.76 6.05 5.58 5.75 5.89 6.01
0
Exp Maxcem Elite RelyX Unicem 2 SpeedCem Plus SmartCEM 2 Calibra Universal
Self-adhesive resin cements
ht-curing (5 min) 4.67 4.71 4.79 5.08 5.06 5.09
-curing (5 min) 3.38 3.07 3.24 3.69
Figure 8.
Figure 8. Volumetric shrinkage for
Volumetric shrinkage for light
light curing at
curing min3.40
at 55 min and self-curing
and at 3.39
self-curing at 55 min
min and
and 60
60 min.
min. (Value
(Value
-curing (60 min) 5.76 6.05 5.58 5.75 5.89 6.01
bars with the same letter are statistically equivalent between the tested groups).
bars with the same letter are statistically equivalent between the tested groups).
Self-adhesive resin cements

Figure 8. Volumetric shrinkage for light curing at 5 min and self-curing at 5 min and 60 min. (Value
bars with the same letter are statistically equivalent between the tested groups).
Polymers 2024,16,
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6
6

(%)
5

(%)
shrinkage
5

shrinkage
4
4
3

Volumetric
3

Volumetric
2
2
1
1
0
0 0 1 2 3 4 5
0 1 2 3 4 5
Time (min)
Time (min)
Exp Maxcem Elite RelyX Unicem 2
Exp Maxcem Elite RelyX Unicem 2
SpeedCem Plus SmartCEM 2 Calibra Universal
SpeedCem Plus SmartCEM 2 Calibra Universal

Figure9.9.Volumetric
Figure Volumetricshrinkage
shrinkageofofself-adhesive
self-adhesiveresin
resincements
cementsover
overtime
timefor
forlight
lightcuring.
curing.
Figure 9. Volumetric shrinkage of self-adhesive resin cements over time for light curing.

7
7
6
6
(%)

5
(%)
shrinkage

5
shrinkage

4
4
3
Volumetric

3
Volumetric

2
2
1
1
0
0 0 10 20 30 40 50 60
0 10 20 30 40 50 60
Time (min)
Time (min)
Exp Maxcem Elite RelyX Unicem 2
Exp Maxcem Elite RelyX Unicem 2
SpeedCem Plus SmartCEM 2 Calibra Universal
SpeedCem Plus SmartCEM 2 Calibra Universal

Figure 10. Volumetric shrinkage of self-adhesive resin cements over time for self-curing.
Figure10.
Figure 10.Volumetric
Volumetricshrinkage
shrinkageofofself-adhesive
self-adhesiveresin
resincements
cementsover
overtime
timefor
forself-curing.
self-curing.
3.1. Effect of Cement Materials on DC under Different Activation Modes
For dual
3.1. Effect curingMaterials
of Cement at differenton DC temperatures,
under Different times, and orders
Activation Modes of self-curing and light
curing, Under
the self-curing for
Experimental SARC5 min had anda 10 min at 23higher
significantly °C andor37higher
°C (Table 1, curing
DC than scenarios
otherscenarios
cements
1–4), Under
the self-curing for
Experimental SARC5 min and 10a min
showed at 23 °C and
significantly 37 °C
higher DC (Table
than 1, curing
other cements (p
(p < 0.001), except SpeedCem Plus at 23 ◦ C and Maxcem Elite and SpeedCem Plus at 37(p ◦ C<
1–4),
0.001);the Experimental
however, SARCitshowed
statistically, was the asame
significantly
as Maxcem higher
EliteDCandthan other cements
SpeedCem Plus◦ for <
10
(p > 0.05)
0.001); (Figure 3)
however, in curing scenarios
statistically, it was the 7same
and 8as(Table
Maxcem1, SCElite
10 minand +SpeedCem
LC 20 s at Plus
23 Cfor and 10
37min◦ at Compared
37 °C (p > 0.05) (Figure 1).
minC). at 37
Under °C (p >
light
to curing
0.05)
curing (Figure
for
scenarios
20 1).
s at 23
7 and 8, the Experimental SARC showed a signifi-
°C and 37 °CSmartCEM
(Table 1, curing scenarios 5 and 6), the
cantlyUnder
higherlightor higher
curingDC for than RelyX
20 s was
at °CUnicem
and 37 2,
23statistically °C (Table 1, 2, andscenarios
curing Calibra Universal
5Elite,
and 6), at
the
DC◦ of the Experimental SARC the same as that
23 C, and it was significantly higher than that of other cements (p < 0.001), except Speed- of Maxcem RelyX
DC of the
Unicem Experimental SARC was statistically the same as that of Maxcem Elite, RelyX
Cem Plus2,(pand SpeedCem
> 0.05) at 37 ◦ CPlus
(Figureat 234) °C and SpeedCem
in curing scenarios Plus
9 andat10both
(LC23 20°Cs +and
SC 1037 min
°C (pat>
Unicem
0.05).
◦ It 2,
wasand◦ SpeedCem
significantly Plus
higher at 23
than °C and SpeedCem
SmartCEM 2 and Plus at
Calibra both 23 °C
Universal and
at 37
23 °C
°C (p >
and
23 C and 37 C). Compared to curing modes 9 and 10, the DC of the Experimental SARC
0.05).
Maxcem It was significantly
Elite, RelyX Unicemhigher2, of than SmartCEM
SmartCEM 2Calibra
and Calibra Universal at 23
(p <°C0.001)
and
was statistically the same as that Maxcem 2, andRelyX
Elite, Universal
Unicem 2, andat SpeedCem
37 °C Plus
Maxcem2). Elite, RelyX Unicem 2, SmartCEM 2, and Calibra Universal at 37 °C (p < 0.001)
(p(Figure
> 0.05), but it was significantly higher than that of SmartCEM 2 and Calibra Universal
(Figure 2).
For dual ◦ C and
(p < 0.001) at 23curing atsignificantly
different temperatures,
higher or higher times,
thanand orders
that of self-curing
of other cements (pand light
< 0.001),
For
curing, dual
the curing
Experimental at different
◦
SARC temperatures,
had a times,higher
significantly and orders
or of self-curing
higher DC than and
other light
ce-
except SpeedCem Plus at 37 C (p > 0.05) (Figure 4) in curing scenarios 11 and 12 (LC 20 s + SC
curing,
ments (pthe
< ◦ Experimental
0.001), ◦
except SARC hadPlus
SpeedCem a significantly
at 23 °C andhigher
Maxcem or higher
Elite DCSpeedCem
and than otherPlus ce-
5 min at 23 C and 37 C).
ments
at 37 °C(p(p< >0.001), except SpeedCem
0.05) (Figure 3) in curingPlus at 23 °C
scenarios and8Maxcem
7 and (Table 1,Elite
SC 10andminSpeedCem
+ LC 20 s at Plus 23
at
°C37and°C37 (p °C).
> 0.05) (Figure 3)toincuring
Compared curingscenarios
scenarios77and and8,8 the
(Table 1, SC 10 min
Experimental + LCshowed
SARC 20 s at 23a
°C and 37 °C).higher
significantly Compared to curing
or higher DC scenarios
than RelyX 7 and 8, the Experimental
Unicem 2, SmartCEMSARC 2, and showed
Calibra a
significantly higher or higher DC than RelyX Unicem 2, SmartCEM 2, and Calibra
Polymers 2024, 16, 581 10 of 15

3.2. Effect of Temperature on DC under Different Activation Modes

For all self-adhesive cements in self-curing (curing scenarios 1–4), the DC at 37 ◦ C was
significantly higher or higher than that at 23 ◦ C (Figure 1). For all self-adhesive cements in
light curing (curing scenarios 5 and 6), there was no statistical difference between 23 ◦ C and
37 ◦ C for any of the self-adhesive cements (Figure 2). For dual curing, the DC at 37 ◦ C was
significantly higher for Maxcem Elite and RelyX Unicem 2 (p < 0.001), and it was higher
for other cements (p > 0.05) than that at 23 ◦ C (Figure 3) in curing scenarios 7 and 8. There
was no statistical difference between 23 ◦ C and 37 ◦ C for any of the cements except the
Experimental SARC (Figure 4) in curing scenarios 9–12.

3.3. Effect of Time on DC under Different Curing Scenarios

All self-adhesive cements showed a significantly higher DC for 10 min than for 5 min
at both 23 ◦ C and 37 ◦ C in self-curing (Figure 1). For all cements under dual curing, there
was no statistical difference between 5 min and 10 min except for the Experimental SARC
and Calibra Universal at 23 ◦ C and RelyX Unicem 2 at 37 ◦ C (p < 0.001) (Figure 4).

3.4. Correlations between the Degree of Conversion and Flexural Strength, Flexural Modulus, and
Water Solubility
Pearson’s correlations between the degree of conversion and flexural strength, flexural
modulus, and water solubility in self-curing (data of flexural strength, flexural modulus,
and water solubility are from our previous study [21]) are shown in Figures 5–7. A strong
or moderate correlation was found between the degree of conversion and flexural strength
(Pearson’s correlation coefficient R = 0.7605), flexural modulus (R = 0.6641), and water
solubility (R = 0.8528) according to Evans’ and Moore’s guide (R > 0.6 or 0.7 indicated
moderate or strong relationship) [28,29].

3.5. Volumetric Shrinkage under Different Curing Modes

There was no statistical difference in volumetric shrinkage among these tested cements
under light curing at 5 min and self-curing at 5 min and 60 min, respectively (Figure 8).
For each cement, the volumetric shrinkage of self-curing was significantly lower than that
of light curing after 5 min at 23 ◦ C (Figure 8). Self-curing showed a slower increase in
volumetric shrinkage than light curing over time (Figures 9 and 10).

4. Discussion
A couple of testing methods have been used to determine the degree of conversion, like
Fourier transform infrared (FTIR) [30–32], Raman spectroscopy [33], Stray-field magnetic reso-
nance imaging (STRAFI-MRI) [34], Photo differential scanning calorimetry (photo-DSC) [35],
etc. FTIR is the most common method for measuring the DC in most studies [30–32], which
was used to determine the DC at various curing scenarios in this study.
Self-curing (auto-polymerization/chemically activated) is essential for most indirect
restorations, especially for metal or ceramo-metal inlays, onlays, crowns and bridges, and
endodontic post, because little or no light is transmittable through the restorative materials.
For all curing scenarios of self-curing (curing scenarios 1–4, 5 min and 10 min at 23 ◦ C
and 37 ◦ C), the Experimental SARC showed a significantly higher or higher DC than other
cements (Figure 1), while RelyX Unicem 2 had the lowest value of DC, which (16.6 ± 0.8% at
23 ◦ C for 10 min) was similar to the values the literature reported (11.05 ± 4.16% at 23 ◦ C for
10 min) [25]. The different values of DC are attributed to the cement composition, primarily
the chemical composition of resin matrices, such as self-curing initiator systems, inhibitors,
and monomers [25,35–37]. Table 2 lists the resin composition of all cements based on the
available information, indicating some differences among these cements. The Experimental
SARC was formulated through our proprietary resin and filler technology, which uses
cumene hydroperoxide/(2,3-difluorophenyl)thiourea as the self-curing initiator system.
RelyX Unicem 2 and SpeedCem Plus contained sodium persulfate and dibenzoyl perox-
ide, respectively [25], whereas no information is available for Maxcem Elite, SmartCEM
Polymers 2024, 16, 581 11 of 15

2, or Calibra Universal. In addition, the acidic monomer, as an important component

of self-adhesive resin cement, influences the initiator system, especially for the initiator
system containing the amine co-initiator [25]. The Experimental SARC and SpeedCem Plus
used 10-methacryloxydecyl dihydrogen phosphate (10-MDP) as a self-etch and adhesive
monomer in their resin composition, while Maxcem Elite, SmartCEM 2, and Calibra Univer-
sal used glycerol phosphate dimethacrylate (GPDM) and dipentaerythritol pentaacrylate
monophosphate (PENTA)/4-methacryloxyethyl trimellitate anhydride (4-META), respec-
tively. The Experimental SARC used cumene hydroperoxide/(2,3-difluorophenyl)thiourea
as self-curing initiators instead of the amine system. All of these resulted in different values
of DC, affecting the cement properties, such as physical and mechanical properties [11–14].
This was proven in this study by a strong correlation between the DC and the flexural
strength (R = 0.7605) or flexural modulus (R = 0.6641) in self-curing (Figures 5 and 6),
i.e., the Experimental SARCs exhibited statistically higher flexural strength and flexural
modulus than other cements, whereas RelyX Unicem 2 had the lowest flexural strength
and flexural modulus among these cements [21].
Clearly, curing temperature and time have a great effect on DC for self-curing (Figure 1).
All self-adhesive cements in the present study showed a significantly higher or higher DC at
37 ◦ C than at 23 ◦ C for both 5 min and 10 min, and the DC for 10 min was significantly higher
than that at 5 min at both 23 ◦ C and 37 ◦ C. It is easily understood that higher temperatures
and longer times will result in more monomers converted to polymers by reducing the
viscosity of the reaction system and increasing the polymerization rate according to the
Arrhenius equation, free radical polymerization theory, and the literature reported [4,38,39].
For light curing at both 23 ◦ C and 37 ◦ C (Figure 2), the DC of the Experimental SARC
and SpeedCem Plus were higher than other cements, and RelyX Unicem 2 had a signifi-
cant increase from self-curing to light curing. The findings are mainly related to the light
curing initiator system [31,40,41]. The Experimental SARC contains both camphorquinone
(CQ, Absmax at 470 nm) and bis(2,4,6-trimethylbenzoyl)-phenyl-phosphineoxide (BTPPO,
Absmax at 365 nm) as photo-initiators, which can cover a wider range of light absorption
from Ultraviolet (UV) to visible (blue) regions (320–500 nm) compared to only CQ used for
some cements [41]. The curing light gun (Bluephase Style, Ivoclar Vivadent AG, Schaan,
Liechtenstein) used in this study can cure without restriction in the wavelength range of
380 to 515 nm. The optimal combination resulted in a higher DC. The other cements, like
SpeedCem Plus, may use other high-efficiency photo-initiator systems, resulting in a higher
DC as well. The results of our previous water solubility test [21] strongly support the differ-
ent performances of DC among these cements. DC has a strong negative relationship with
water solubility in this study [Figure 7], i.e., the higher the DC, the less monomers existed,
which formed more densely cross-linked networks and thus resulted in the potentially
lower water solubility.
For all self-adhesive cements under light curing (curing scenarios 5 and 6), there was
no statistical difference between 23 ◦ C and 37 ◦ C (Figure 2), indicating that temperature
did not affect the DC between room temperature (23 ◦ C) and oral temperature (37 ◦ C).
Compared to self-curing, all cements had a significantly higher DC in light curing for
20 s at 23 ◦ C and 37 ◦ C (curing scenarios 5 and 6) than in self-curing for 5 min at 23 ◦ C
(curing scenario 1), whereas each cement behaved differently compared to other self-curing
scenarios (curing scenario 2–4, 10 min at 23 ◦ C and 5 min and 10 min at 37 ◦ C). For example,
only RelyX Unicem 2 showed a significantly higher DC in light curing than in all scenarios
of self-curing, which means that RelyX Unicem 2 depends mainly on photoactivation and
needs a longer time at oral temperature if self-cured. The DCs of the Experimental SARC
for light curing at 23 ◦ C and 37 ◦ C were lower than the self-curing DC for 10 min at 23 ◦ C
and 37 ◦ C, respectively, which was similar to 5 min at 37 ◦ C and higher than 5 min at 23 ◦ C.
Resin cements were developed in dual-cure activation mode to ensure higher curing
efficiency (a higher DC) for various restorations by combining the benefits of both light
curing and self-curing to obtain favorable physical, mechanical, and bonding properties [25].
For all cements, each cement had a significantly higher or higher dual-curing DC (curing
Polymers 2024, 16, 581 12 of 15

scenarios 7–12) than its corresponding self-curing DC (curing scenarios 1–4), except that
statistically, the Experimental cement and the Maxcem Elite had the same DC for self-curing
for 10 min at 37 ◦ C (scenario 4) as first self-curing for 10 min and then light curing for
20 s at 23 ◦ C (scenario 7) (Experimental and Maxcem Elite) and first light curing for 20 s
and then 5 min of self-curing (scenario 11) (Experimental). The results of this study are in
agreement with other studies reported, which indicated that dual-curing mode is more
effective than self-curing mode, i.e., generally, dual curing has a much higher DC than
self-curing [25,42]. The Experimental cement exhibited a significantly higher or higher DC
than other cements except, statistically, the same value as SpeedCem Plus in dual-curing
mode, but the difference in the DC between the Experimental cement and other cements
decreased compared to self-curing mode due to the stronger energetic curing promoted by
light curing. In addition, the order of self-curing and light curing (immediate or delayed
light curing) in the dual-curing mode also affects the DC. The DC of immediate light curing
(first 20 s of light curing and then 10 min of self-curing, curing scenarios 9 and 10) in
this study was slightly higher or higher than that of delayed light curing (first 10 min of
self-curing and then 20 s of light curing, curing scenarios 7 and 8) when cements started
to mix, depending on the materials (composition), temperature, time, etc. [34,43]. This is
because light curing has a much higher polymerization rate than self-curing, and it can
quickly reach a high monomer conversion (DC) due to the different initiator systems when
cements are immediately exposed to light once mixed [43].
Shrinkage is widely recognized as an inherent phenomenon in polymerizable monomer
resins when polymerization occurs [18–20]. There have been different methods to measure
the volumetric shrinkage of composite resins, such as the use of the mercury dilatometer,
the Archimedes method, and the video imaging method [44–48]. AcuVol is a video imag-
ing measurement system that allows for noncontact visual analysis of volume changes
in small-volume samples, and it determines volumetric shrinkage in real time based on
optical measurements and pattern recognition [47,48]. Analysis can be conducted in actual
volume units and as percentage changes in volume. Volumetric shrinkage in this study
was evaluated using AcuVol.
The volumetric shrinkage of the Experimental cement was statistically the same as
that of other cements under light curing at 5 min and self-curing at 5 min and 60 min,
respectively (Figure 8). The volumetric shrinkage mainly depends on the composition of
the resin cements under the same curing conditions, i.e., the resin matrix, such as monomer
type/structure and initiators, and the filler, such as loading, type, and size [49–52]. Based
on the limited information provided by the manufacturers regarding the composition of
the tested self-adhesive cements (Table 2), most cements have the same or similar filler
loading (69–70%), yet some of the fillers and resins are the same, such as barium boron
fluoroaluminosilicate, amorphous silicon dioxide, and urethane dimethacrylate (UDMA);
this is probably the major reason that these cements showed similar volumetric shrinkage
under light curing and self-curing.
Like resin-based composites, manufacturers have tried to develop low-shrinkage,
self-adhesive cements to reduce the risk of marginal leakage and bonding failure while
achieving a proper or higher DC. A higher DC often follows higher shrinkage, which causes
increased shrinkage stress that could exceed the bond strength between the tooth structure
and the restoration substrate, resulting in potential de-bonding/cementation failure [11,53].
As an increasing DC leads to increased shrinkage, an optimal DC and minimal shrinkage
are expected and can be possibly achieved by optimizing the composition of resin ma-
terials (monomer structure and filler, curing technology, etc.) [53,54]. The Experimental
SARC was formulated using our proprietary resin and filler technology, which is based on
low-shrinkage monomers, such as ethoxylated bisphenol A dimethacrylate with higher
molecular weight and lower viscosity, with consideration of physical, mechanical, and ad-
hesive properties. A higher DC was obtained with similar volumetric shrinkage compared
to other cements. Clearly, the volumetric shrinkage of self-curing is significantly lower
than that of light curing for all cements at 5 min (Figure 8), and self-curing has a lower
Polymers 2024, 16, 581 13 of 15

polymerization rate than light curing (Figures 8 and 9), which is in agreement with previous
studies due to the difference in the initiator system and the curing mode/mechanism of
self-curing and light curing [38,52,55].
The limitation is that this study did not consider the polymerization kinetics of
monomer conversion, like the rate of polymerization, and polymerization shrinkage stress.
Future work will focus on these investigations.

5. Conclusions
The hypothesis has been proven, i.e., a newly developed, self-adhesive resin cement
exhibited a higher degree of conversion and similar volumetric shrinkage compared to
the commercial self-adhesive resin cements based on the findings of this study for the
degree of conversion and volumetric shrinkage. Experimental self-adhesive resin cement is
a good alternative to a simplified clinic bonding procedure for the cementation of indirect
restoration.

Author Contributions: Conceptualization, methodology, writing—original draft preparation, L.L.;

supervision, L.L. and R.M.; formal analysis, investigation, data curation, L.L. and Y.C.; validation,
resources, L.L., Y.C. and R.M.; writing—review and editing, L.L.; project administration, R.M.; funding
acquisition, R.M. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Data Availability Statement: Data are contained in the article.
Conflicts of Interest: The authors are employed by Glidewell Dental.

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