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Department of Orthodontics, School of Stomatology, Capital Medical University, Beijing, 100050, China
1
Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing, China
2
PETG/PC/TPU polymer blend was prepared by mechanical blending. The mechanical properties of modified PETG/PC/TPU blend
were characterized using a universal testing machine, and results were compared against two commercial thermoplastic products
—Erkodur and Biolon. Blending modification improved the properties of PETG/PC/TPU. When blending ratio (wt%) was 70/10/20,
PETG/PC/TPU exhibited optimal mechanical properties which exceeded those of Erkodur and Biolon. Tear strength was 50.23 MPa
and elongation at break was 155.99%. Stress relaxation rate was 0.0136 N/s after 1 hour, which was significantly slower than
Erkodur and Biolon (p<0.05). Water absorption rate was 0.57% after 2 weeks, which was significantly lower than Erkodur and Biolon
(p<0.05).
applications run the gamut from engineering materials Erkodur (1.0 mm thickness; Erkodent Erich Kopp
and coatings to adhesives and films16,17). GmbH, Pfalzgrafenweiler, Germany) and Biolon (1.0 mm
Polymer blending has been accepted as an efficient thickness; Dreve Dentamid GmbH, Unna, Germany) are
and inexpensive method of polymer property two widely used commercial thermoplastic products.
diversification18,19). To obtain a useful product with a They were used in this study for benchmarking
satisfactory level of cohesion, various structural comparison of the mechanical properties of the prepared
considerations of the blend partners should be considered polymer blend materials.
so as to obtain a blend that may be classified as miscible
or mechanically compatible20). To date, a considerable Tear strength measurement
amount of literature on polyester blends has been Rectangular specimens, 5 mm×40 mm, of each polymer
published: PETG/PET, PETG/LCP, PC/ABS, PC/PP, blend material were prepared for tear strength testing.
TPU/PVDF, TPU/PP, and TPU/PMMA10,17,21-25). These The tear strengths of all rectangular test specimens were
studies showed that polymer blending was indeed an measured according to ASTM guideline D624-00, which
effective way to improve the mechanical properties of measures the force required to completely rupture across
polymers, eventually culminating in a high-performance the width of a material26). Tear strength testing was
engineering material. carried out using a universal testing machine (Model
The objective of this study was to improve the 3300, Instron, Norwood, MA, USA) at room temperature
mechanical properties of PETG/PC/TPU polymer blend and at a crosshead speed of 10 mm/min. For each
by blending modification to meet the list of critical polymer blend material, the mean value of five test
characteristics required of invisible orthodontic specimens was calculated.
appliances. The mechanical properties of the prepared
PETG/PC/TPU polymer blend were characterized and Stress relaxation measurement
then compared against those of two commercial Rectangular specimens, 5 mm×40 mm, of each polymer
thermoplastic products, Erkodur and Biolon. blend material were prepared for stress relaxation
testing. Dimensions of the test specimens before and
after stress relaxation testing were taken according to
MATERIALS AND METHODS
ASTM guideline D624-00. Using a universal testing
Raw materials for polymer blending machine, all test specimens were loaded at room
Three polymers were selected as raw materials to temperature to reach a 5% strain. They were then
prepare the polymer blends in this study: poly(ethylene unloaded and allowed to recover for 60 minutes (i.e.,
terephthalate)-glycol with a molecular weight of 26,000 3600 seconds). Stress relaxation rate was calculated as
(PETG; DN011, Eastman Chemical Co., Tennessee, follows: (N0–N1)/3600, where N1 is the residual stress of
USA), polycarbonate with a molecular weight of 23,500 specimen after 60 mins and N0 is the initial stress before
(PC; P5001, Unitika, Osaka, Japan), and thermoplastic stress relaxation testing. For each polymer blend
polyurethane with a molecular weight of 18,000 (TPU; material, the mean value of five test specimens was
345X, Bayer, Leverkusen, Germany). They were calculated.
supplied in the form of translucent, colorless pellets.
Three types of polymer blends were prepared in this Water absorption measurement
study: PETG/PC, PETG/TPU, and PETG/PC/TPU. For Rectangular specimens, 50 mm×50 mm, of each polymer
each type of polymer blend, five different blending ratios blend material were prepared for water absorption test.
(wt%) were used. For PETG/PC, the five blending ratios Specimens were stored in a desiccator to reach a constant
of PETG to PC were: 100/0, 90/10, 80/20, 60/40, and 40/60 weight (W0) before they were immersed in distilled water
(w/w). For PETG/TPU, the five blending ratios of PETG at 37°C. To measure weight gain ratio, specimens were
to TPU were: 100/0, 95/5, 90/10, 85/15, and 80/20 (w/w). periodically retrieved from the water at 6, 12, 24, 48,
For PETG/PC/TPU, the five blending ratios in respective 168, and 336 h after immersion began. At each retrieval,
orders were: 80/10/10, 70/10/20, 60/10/30, 50/10/40, and specimen was wrapped in filter paper to absorb water
40/10/50. from the surface and then weighed using an electronic
Polymer blend specimens were obtained by injection balance. Reading accuracy was 0.1 mg and variation in
molding process in accordance with ISO standard 527-2 specimen weight was less than 0.12%.
type 1A. Before injection molding, the pellets were dried Percent increase in weight (%) was calculated as
in an oven for 6 h at a temperature of 80°C. Table 1 follows: [(Wt−W0)/W0]×100, where Wt is the specimen
summarizes the injection molding conditions used in this weight at immersion time t and W0 is the initial specimen
study. weight before immersion. Percentage of water absorbed
was calculated to the nearest 0.01%. For each polymer PETG/PC/TPU and Erkodur or Biolon (p>0.05).
blend material, the mean value of five test specimens
was calculated. Stress relaxation rate
Tables 2–4 show the stress relaxation rates of PETG/PC,
Statistical analysis PETG/TPU, and PETG/PC/TPU respectively.
All recorded values were analyzed using a statistical When PETG was blended with PC, stress relaxation
software (SPSS v.15.0, SPSS Inc., Chicago, IL, USA). rate increased with increasing blend ratio of PC (Table
Data are presented as mean value±standard deviation in 2). When PETG was blended with TPU, stress relaxation
Tables 2–5. One-way ANOVA was used to determine the rate decreased with increasing blend ratio of TPU (Table
presence of statistically significant differences between 3). At the blending ratio of 70/10/20, stress relaxation
different polymer blend materials and commercial rate of PETG/PC/TPU was 0.0136 N/s after 1 hour, which
thermoplastic products. was slower than Erkodur and Biolon (p=0.024 and 0.018)
(Table 4).
RESULTS
Water absorption rate
Tear strength Table 5 shows the water absorption behaviors of the
Tables 2–4 show the tear strength and elongation at different blending ratios of PETG/PC/TPU at different
break results of PETG/PC, PETG/TPU, and PETG/PC/ immersion times in comparison with Erkodur and
TPU respectively. Biolon. During the first 48 hours of immersion, water
When PETG was blended with PC, tear strength absorption rate was rather high for both the commercial
increased with increasing blend ratio of PC but products and PETG/PC/TPU at all blending ratios. This
elongation-at-break value decreased (Table 2). When was followed by a slowdown and eventually a plateau
PETG was blended with TPU, elongation-at-break value after 2 weeks of immersion.
increased with increasing blend ratio of TPU but tear Despite a general trend in water absorption behavior
strength decreased (Table 3). At the blending ratio of for the tested materials over a 2-week immersion period,
70/10/20 for PETG/PC/TPU, optimal values were it was observed that the water absorption rate of PETG/
reached: tear strength was 50.23 MPa and elongation at PC/TPU increased with an increase in TPU blending
break was 155.99% (Table 4). At this blending ratio, ratio. At 2 weeks, there were no statistically significant
there were no statistically significant differences between differences between the blending ratios of 80/10/10 and
Table 2 Comparison of mechanical properties of PETG/PC at different blending ratios (n=5, x±s)
PETG/PC Tear strength (MPa) Elongation at break (%) Stress relaxation rate (N/s)
100/ 0 45.12 (2.15)a 141.22 (4.85)a 0.0192 (0.0005)ab
90/10 52.94 (2.44) b
111.65 (4.11) ab
0.0266 (0.0009)ab
80/20 54.33 (2.31)b 105.21 (3.84)ab 0.0288 (0.0006)ab
60/40 59.63 (2.05) ab
94.93 (3.81) ab
0.0301 (0.0006)ab
40/60 61.54 (2.91)ab 86.62 (3.47)ab 0.0356 (0.0008)ab
Erkodur 54.62 (2.56) 150.16 (5.26) 0.0148 (0.0006)
Biolon 48.56 (2.85) 145.22 (4.94) 0.0153 (0.0004)
a
Significantly different from Erkodur by one-way ANOVA (p<0.05).
b
Significantly different from Biolon by one-way ANOVA (p<0.05).
Table 3 Comparison of mechanical properties of PETG/TPU at different blending ratios (n=5, x±s)
PETG/TPU Tear strength (MPa) Elongation at break (%) Stress relaxation rate (N/s)
100/0 45.12 (2.15) a
141.22 (4.85) a
0.0192 (0.0005)ab
95/5 44.25 (2.32)ab 148.88 (5.15) 0.0181 (0.0005)ab
90/10 44.01 (2.02) ab
151.62 (5.31) b
0.0168 (0.0007)ab
85/15 43.25 (2.18)ab 157.61 (5.77)ab 0.0151 (0.0003)
80/20 42.52 (2.07) ab
158.72 (5.62) ab
0.0131 (0.0005)ab
Erkodur 54.62 (2.56) 150.16 (5.26) 0.0148 (0.0006)
Biolon 48.56 (2.85) 145.22 (4.94) 0.0153 (0.0004)
a
Significantly different from Erkodur by one-way ANOVA (p<0.05).
b
Significantly different from Biolon by one-way ANOVA (p<0.05).
Dent Mater J 2011; 30(6): 954–959 957
Table 4 Comparison of mechanical properties of PETG/PC/TPU at different blending ratios (n=5, x±s)
PETG/PC/TPU Tear strength (MPa) Elongation at break (%) Stress relaxation rate (N/s)
80/10/10 52.83 (2.55) b
135.25 (3.82) ab
0.0172 (0.0004)ab
70/10/20 50.23 (2.43) 155.99 (5.65) ab
0.0136 (0.0002)ab
60/10/30 47.07 (2.57)a 169.31 (6.85)ab 0.0121 (0.0006)ab
50/10/40 42.77 (2.31)ab 171.37 (6.41)ab 0.0113 (0.0003)ab
40/10/50 34.98 (1.85) ab
182.57 (7.13) ab
0.0098 (0.0002)ab
Erkodur 54.62 (2.56) 150.16 (5.26) 0.0148 (0.0006)
Biolon 48.56 (2.85) 145.22 (4.94) 0.0153 (0.0004)
a
Significantly different from Erkodur by one-way ANOVA (p<0.05).
b
Significantly different from Biolon by one-way ANOVA (p<0.05).
Table 5 Comparison of water absorption rates of PETG/PC/TPU at different blending ratios (% weight increase)
PETG/PC/TPU 6h 12 h 24 h 48 h 168 h 336 h
80/10/10 0.15 (0.013)ab 0.18 (0.019)ab 0.28 (0.027)ab 0.40 (0.047)ab 0.51 (0.026)ab 0.52 (0.021)ab
70/10/20 0.12 (0.014)ab 0.22 (0.021)ab 0.33 (0.033)ab 0.42 (0.031)ab 0.53 (0.033)ab 0.57 (0.023)ab
60/10/30 0.17 (0.016)ab 0.23 (0.015)ab 0.30 (0.031)ab 0.51 (0.058)ab 0.64 (0.021)ab 0.67 (0.024)ab
50/10/40 0.12 (0.011)ab
0.21 (0.026) ab
0.31 (0.026) ab
0.51 (0.023) ab
0.67 (0.028) ab
0.72 (0.026)ab
40/10/50 0.14 (0.017)ab 0.21 (0.031)ab 0.29 (0.028)ab 0.53 (0.021)ab 0.72 (0.036)ab 0.73 (0.035)ab
Erkodur 0.34 (0.021) 0.43 (0.044) 0.58 (0.017) 0.72 (0.037) 0.76 (0.029) 0.80 (0.027)
Biolon 0.33 (0.025) 0.45 (0.015) 0.58 (0.023) 0.73 (0.020) 0.78 (0.018) 0.81 (0.015)
a
Significantly different from Erkodur by one-way ANOVA (p<0.05).
b
Significantly different from Biolon by one-way ANOVA (p<0.05).
70/10/20 (p=0.992). However, there were significant bring about tooth movement. Therefore, it is critically
differences between the blending ratios of 80/10/10 and important to have a thorough understanding of the effect
70/10/20 and the other three blending ratios (p<0.05). of long-term loading on the mechanical properties of
When compared with the commercial products, PETG/ thermoplastic polymers. This helps to assess if a
PC/TPU at 70/10/20 blending ratio exhibited 0.57% particular thermoplastic material could fulfill the
water absorption rate after 2 weeks, which was purpose of an orthodontic appliance in providing light,
significantly lower than Erkodur and Biolon (p=0.002 sustained orthodontic forces9) to accomplish effective
and 0.001). tooth movement. A thermoplastic material is viscoelastic
in nature, which means that the force generated by the
programmed movement decreases as a function of time.
DISCUSSION
Therefore, we seek a thermoplastic material that exhibits
Thermoplastic polymers are used as structural materials substantial linear elastic behavior with a high yield
in the fabrication of clear orthodontic appliances. In the point.
mouth, orthodontic appliances are subjected to both Polyester, polyurethane, and polypropylene are the
short-term and long-term loading forces27). For example, dominant thermoplastic materials used in the fabrication
a short-term load is encountered when an orthodontic of clear orthodontic appliances. Amongst which, PET is
appliance is fitted over a patient’s teeth. The appliance a widely used thermoplastic material because it has good
may undergo severe deformation during fitting, but a creep properties, fatigue resistance, and dimensional
clear orthodontic appliance responds in an elastic stability10). However, our preliminary study revealed
manner by returning to its original shape after the that the mechanical properties of PET were inferior to
short-term loading force causing the deformation is two commercial thermoplastic products, Erkodur and
removed. Once fitted over the patient’s teeth, the Biolon. To improve the mechanical properties of PET,
appliance is subjected to long-term loading forces exerted styrene-ethylene-butylene-styrene block copolymer
intermittently upon it between meals and when worn (SEBS) and ethylene-propylene-diene monomer (EPDM)
overnight. were blended with PET to produce a polymer blend.
Though subjected to long-term loading in the mouth, Blending modification yielded a polymer blend with an
a clear thermoplastic appliance should nonetheless exert opaque appearance and a lower rebound resilience. Both
continuous, controlled, orthodontic forces on teeth to characteristics did not meet the criteria for invisible
958 Dent Mater J 2011; 30(6): 954–959
evaluating the efficacy of tooth movement with Invisalign. 23) Torres RA, Arellano-Ceja J, Hernández-Hernández ME,
Am J Orthod Dentofacial Orthop 2009; 135: 27-35. González-Núñez, R. Effects of the blending sequence and
8) Baldwin DK, King G, Ramsay DS, Huang G, Bollen AM. interfacial agent on the morphology and mechanical
Activation time and material stiffness of sequential removable properties of injection molded PC/PP Blends. Polym Bull
orthodontic appliances. Part 3: Premolar extraction patients. 2007; 59: 251-260.
Am J Orthod Dentofacial Orthop 2008; 133: 837-845. 24) Ma H, Yang Y. Rheology morphology and mechanical
9) Kapila S, Sachdeva R. Mechanical properties and clinical properties of compatibilized poly(vinylidene fluoride) (PVDF)/
applications of orthodontic wires. Am J Orthod Dentofacial thermoplastic polyurethane (TPU) blends. Polym Test 2008;
Orthop 1989; 96: 100-109. 27: 441-446.
10) Dupaix RB, Boyce MC. Finite strain behavior of poly(ethylene 25) Poomali, Siddaramaiah, Suresha B, Lee JH. Mechanical and
terephthalate) (PET) and poly(ethylene terephthalate)-glycol three-body abrasive wear behaviour of PMMA/TPU blends.
(PETG). Polymer 2005; 46: 4827-4838. Mater Sci Eng A 2008; 492: 486-490.
11) Gorlier E, Haudin JM, Billon N. Strain-induced crystallization 26) ASTM D 624-00 (2000; R2007). Standard test method for tear
in bulk amorphous PET under uniaxial loading. Polymer strength of conventional vulcanized rubber and thermoplastic
2001; 42: 9541-9549. elastomers. ASTM International, 2000 (Reapproved 2007).
12) Kattan M, Dargent E, Ledru J, Grenet J. Strain-induced 27) Tuncay OC. The Invisalign System. Quintessence Publishing
crystallization in uniaxially drawn PETG plates. J Appl Co., Ltd., Philadelphia, 2006; pp.177-184.
Polym Sci 2001; 81: 3405-3412. 28) Proffit WR. Contemporary orthodontics, 3rd ed. Mosby, St
13) LeGrand DG, Bendler JT. Handbook of Polycarbonate Louis, 2000. p 304.
Science and Technology. Marcel Dekker Inc., New York, 29) Hahn W, Dathe H, Fialka-Fricke J, Fricke-Zech S, Zapf A,
1999; pp.33-41. Kubein-Meesenburg D, Sadat-Khonsari R. Influence of
14) Cho K, Yang J, Kang BI, Park CE. Notch sensitivity of thermoplastic appliance thickness on the magnitude of force
polycarbonate and toughened polycarbonate. J Appl Polym delivered to a maxillary central incisor during tipping. Am J
Sci 2003; 89: 31-39. Orthod Dentofacial Orthop 2009; 136: 12-19.
15) Yoon PJ, Hunter DL, Paul DR. Polycarbonate nanocomposites. 30) Barbagallo LJ, Shen G, Jones AS, Swain MV, Petocz P,
Part l: Effect of organoclay structure on morphology and Darendeliler MA. A novel pressure film approach for
properties. Polymer 2003; 44: 5323-5339. determining the force imparted by clear removable
16) Frick A, Rochman A. Characterization of TPU-elastomers by thermoplastic appliances. Ann Biomed Eng 2008; 36:
thermal analysis (DSC). Polym Test 2004; 23; 413-417. 335-341.
17) Lu QW, Macosko CW. Comparing the compatibility of various 31) Boubakri A, Haddar N, Elleuch K, Bienvenu Y. Impact of
functionalized polypropylenes with thermoplastic aging conditions on mechanical properties of thermoplastic
polyurethane (TPU). Polymer 2004; 45: 1981-1991. polyurethane. Mater Des 2010; 31: 4194-4201.
18) Paul DR, Newman S. Polymer blends, Vols 1 and 2. Academic 32) Weibin G, Shimin H, Minjiao Y, Long J, Yi D. The effects of
Press, New York, 1978; pp.98-102. hydrothermal aging on properties and structure of bisphenol
19) Utracki LA. Polymer alloys and blends. Hanser, Munich, A polycarbonate. Polym Degrad Stab 2009; 94: 13-17.
1989; pp.44-51. 33) De Nève B, Shanahan MER. Water absorption by an epoxy
20) Olabisi O, Robeson LM, Shaw MT. Polymer-polymer resin and its effect on the mechanical properties and infra-red
miscibility. Academic Press, New York, 1979; pp.33-40. spectra. Polymer 1993; 34: 5099-5105.
21) Hwang SH, Jeong KS, Jung JC. Thermal and mechanical 34) Boubakri A, Elleuch K, Guermazi N, Ayedi HF. Investigations
properties of amorphous copolyester (PETG)/LCP blends. on hygrothermal aging of thermoplastic polyurethane
Eur Polym J 1999; 35: 1439-1443. material. Mater Des 2009; 30: 3958-3965.
22) Sohn JI, Lim ST, Park SH, Choi HJ, Jhon MS. Effect of a 35) Gould TE, Piland SG, Shin J, Hoyle CE, Nazarenko S.
reactive-type flame retardant on the rheological and Characterization of mouthguard materials: physical and
mechanical properties of PC/ABS blends. J Mater Sci 2003; mechanical properties of commercialized products. Dent
38: 1485-1491. Mater 2009; 25: 771-780.