

FOLLOWUS
a.State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
b.Engineering Research Center of Elastomer Materials Energy Conservation and Resources, Ministry of Education, Beijing 100029, China
c.Key Laboratory of Carbon Fiber and Functional polymers, Beijing University of Chemical Technology, Beijing 100029, China
d.Center of Advanced Elastomer Materials, College of Material Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
wangrg@mail.buct.edu.cn (R.G.W.)
lifz@mail.buct.edu.cn (F.Z.L.)
luyonglai@mail.buct.edu.cn (Y.L.L.)
Received:12 September 2024,
Revised:2024-10-11,
Accepted:15 October 2024,
Online First:18 January 2025,
Published:01 February 2025
Scan QR Code
Jin, G. Z.; Chen, L. H.; Gong, Y. Z.; Li, P.; Wang, R. G.; Li, F. Z.; Lu, Y. L. Impact of hard segment structures on fatigue threshold of casting polyurethane using cutting method. Chinese J. Polym. Sci. 2025, 43, 303–315
Guang-Zhi Jin, Le-Hang Chen, Yu-Zhen Gong, et al. Impact of Hard Segment Structures on Fatigue Threshold of Casting Polyurethane Using Cutting Method[J]. Chinese Journal of Polymer Science, 2025, 43(2): 303-315.
Jin, G. Z.; Chen, L. H.; Gong, Y. Z.; Li, P.; Wang, R. G.; Li, F. Z.; Lu, Y. L. Impact of hard segment structures on fatigue threshold of casting polyurethane using cutting method. Chinese J. Polym. Sci. 2025, 43, 303–315 DOI: 10.1007/s10118-025-3250-9.
Guang-Zhi Jin, Le-Hang Chen, Yu-Zhen Gong, et al. Impact of Hard Segment Structures on Fatigue Threshold of Casting Polyurethane Using Cutting Method[J]. Chinese Journal of Polymer Science, 2025, 43(2): 303-315. DOI: 10.1007/s10118-025-3250-9.
The PPDI-CPU exhibits a more regular microstructure with larger
denser spherulites
which enhances stress distribution and inhibits crack propagation
resulting in superior fatigue performance. In contrast
the NDI-CPU shows sparser spherulite distribution
while TDI-CPU lacks a distinct spherulitic structure.
The fatigue resistance of casting polyurethane (CPU) is crucial in various sectors
such as construction
healthcare
and the automotive industry. Despite its importance
no studies have reported on the fatigue threshold of CPU. This study employed an advanced Intrinsic Strength Analyzer (ISA) to evaluate the fatigue threshold of CPUs
systematically exploring the effects of three types of isocyanates (PPDI
NDI
TDI) that contribute to hard segment structures based on the cutting method. Employing multiple advanced characte
rization techniques (XRD
TEM
DSC
AFM)
the results indicate that PPDI-based polyurethane exhibits the highest fatigue threshold (182.89 J/m
2
) due to a highest phase separation and a densely packed spherulitic structure
although the hydrogen bonding degree is the lowest (48.3%). Conversely
NDI-based polyurethane
despite having the high hydrogen bonding degree (53.6%)
exhibits moderate fatigue performance (122.52 J/m
2
)
likely due to a more scattered microstructure. TDI-based polyurethane
with the highest hydrogen bonding degree (59.1%) but absence of spherulitic structure
shows the lowest fatigue threshold (46.43 J/m
2
). Compared to common rubbers (NR
NBR
EPDM
BR)
the superior fatigue performance of CPU is attributed to its well-organized microstructure
polyurethane possesses a higher fatigue threshold due to its high phase separation degree and orderly and dense spherulitic structure which enhances energy dissipation and reduces crack propagation.
Yu, X.; Yuan, Y.; Liang, C.; Wang, X.; Wang, S.; Deng, Z. Development and characterization of high friction polyurethane bearings for bridge engineering applications. Constr. Build. Mater. 2024 , 438 , 136846..
Samad, A.; Siew, W. H.; Given, M.; Liggat, J.; Timoshkin, I. Investigating the impact of hardness on dielectric breakdown characteristics of polyurethane. ACS Omega 2024 , 9 , 24538−24545..
Król, P.; Pilch-Pitera, B. Phase structure and thermal stability of crosslinked polyurethane elastomers based on well-defined prepolymers. J. Appl. Polym. Sci. 2007 , 104 , 1464−1474..
Peebles, L. H., Jr. Sequence length distribution in segmented block copolymers. Macromolecules 1974 , 7 , 872−882..
Cui, Y.; Wang, H.; Pan, H.; Yan, T.; Zong, C. The effect of mixed soft segment on the microstructure of thermoplastic polyurethane. J. Appl. Polym. Sci. 2021 , 138 , 51346..
Chang, Z.; Fahs, G. B.; Hudson, A. G.; Orler, E. B.; Moore, R. B.; Wilkes, G. L.; Turner, S. R. Synthesis and properties of segmented polyurethanes with triptycene units in the soft segment. Macromol. Chem. Phys. 2015 , 216 , 1180−1191..
Sheth, J. P.; Aneja, A.; Wilkes, G. L.; Yilgor, E.; Atilla, G. E.; Yilgor, I.; Beyer, F. L. Influence of system variables on the morphological and dynamic mechanical behavior of polydimethylsiloxane based segmented polyurethane and polyurea copolymers: a comparative perspective. Polymer 2004 , 45 , 6919−6932..
Pangon, A.; Dillon, G. P.; Runt, J. Influence of mixed soft segments on microphase separation of polyurea elastomers. Polymer 2014 , 55 , 1837−1844..
Petcharoen, K.; Sirivat, A. Electrostrictive properties of thermoplastic polyurethane elastomer: effects of urethane type and soft-hard segment composition. Curr. Appl. Phys. 2013 , 13 , 1119−1127..
Das, S.; Cox, D. F.; Wilkes, G. L.; Klinedinst, D. B.; Yilgor, I.; Yilgor, E.; Beyer, F. L. Effect of symmet ry and H-bond strength of hard segments on the structure-property relationships of segmented, nonchain extended polyurethanes and polyureas. J. Macromol. Sci. B 2007 , 46 , 853−875..
Li, X.; Lu, Y.; Wang, H.; Pöselt, E.; Eling, B.; Men, Y. Crystallization of hard segments in MDI/BD-based polyurethanes deformed at elevated temperature and their dependence on the MDI/BD content. Eur. Polym. J. 2017 , 97 , 423−436..
. Corcuera, M. A.; Rueda, L.; Saralegui, A.; Martín, M. D.; Fernández-d'Arlas, B.; Mondragon, I.; Eceiza, A. Effect of diisocyanate structure on the properties and microstructure of polyurethanes based on polyols derived from renewable resources. J. Appl. Polym. Sci. 2011, 122 (6), 3677-3685..
Luo, Y.-L.; Gao, W.-T.; Luo, Z.-Y.; Li, C.-H. Toward mechanically robust self-healing polyurethanes using dynamics chemistry. Mater. Chem. Front. 2024 , 8 , 1767−1791..
Imre, B.; Gojzewski, H.; Check, C.; Chartoff, R.; Vancso, G. J. Properties and phase structure of polycaprolactone-based segmented polyurethanes with varying hard and soft segments: effects of processing conditions. Macromol. Chem. Phys. 2018 , 219 , 1700214..
Candau, N.; Stoclet, G.; Tahon, J.-F.; Demongeot, A.; Yilgor, E.; Yilgor, I.; Menceloglu, Y. Z.; Oguz, O. Mechanical reinforcement and memory effect of strain-induced soft segment crystals in thermoplastic polyurethane-urea elastomers. Polymer 2021 , 223 , 123708..
Ding, J.; Ye, L. Mechanical and solvent-resistance properties of casting polyurethane elastomers. J. Macromol. Sci. B 2012 , 51 , 1125−1138..
Wang, S.; Yuan, Y.; Tan, P.; Zhu, H.; Luo, K. Experimental study on mechanical properties of casting high-capacity polyurethane elastomeric bearings. Constr. Build. Mater. 2020 , 265 , 120725..
Zhang, P.; Zhang, G.; Pan, J.; Ma, C.; Zhang, G. Non-isocyanate polyurethane coating with high hardness, superior flexibility, and strong substrate adhesion. ACS Appl. Mater. Interfaces 2023 , 15 , 5998−6004..
Nagy, L.; Vadkerti, B.; Lakatos, C.; Fehér, P. P.; Zsuga, M.; Kéki, S. Kinetically equivalent functionality and reactivity of commonly used biocompatible polyurethane crosslinking agents. Int. J. Mol. Sci. 2021 , 22 , 4059..
Tae Moon, H.; Lee, Y. K.; Koo Han, J.; Byun, Y. A novel formulation for controlled release of heparin-DOCA conjugate dispersed as nanoparticles in polyurethane film. Biomaterials 2001 , 22 , 281−289..
Yu, X.; Shi, M.; Wang, X.; Yuan, Y.; Wang, S.; Deng, Z.; Zhu, H. Effect of water immersion on the seismic isolation performance of castable polyurethane bearing. Constr. Build. Mater. 2024 , 412 , 134660..
Li, J.; Hutchings, I. M. Resistance of cast polyurethane elastomers to solid particle erosion. Wear 1990 , 135 , 293−303..
Oprea, S.; Potolinca, V. O.; Oprea, V. Synthesis and properties of new crosslinked polyurethane elastomers based on isosorbide. Eur. Polym. J. 2016 , 83 , 161−172..
Ammam, M.; Fransaer, J. Highly sensitive and selective glutamate microbiosensor based on cast polyurethane/AC-electrophoresis deposited multiwalled carbon nanotubes and then glutamate oxidase/electrosynthesized polypyrrole/Pt electrode. Biosens.Bioelectron. 2010 , 25 , 1597−1602..
Koyama, A.; Suetsugu, D.; Fukubayashi, Y.; Mitabe, H. Experimental study on the dynamic properties of rigid polyurethane foam in stress-controlled cyclic uniaxial tests. Constr. Build. Mater. 2022 , 321 , 126377..
Choi, E.; Lee, J. S.; Jeon, H. K.; Park, T.; Kim, H. T. Static and dynamic behavior of disk bearings for OSPG railway bridges under railway vehicle loading. Nonlinear Dyn. 2010 , 62 , 73−93..
Jamil, A.; Guan, Z. W.; Cantwell, W. J. The static and dynamic response of CFRP tube reinforced polyurethane. Compos. Struct. 2017 , 161 , 85−92..
Zhang, W.; Hu, J.; Tang, J.; Wang, Z.; Wang, J.; Lu, T.; Suo, Z. Fracture toughness and fatigue threshold of tough hydrogels. ACS Macro Lett. 2019 , 8 , 17−23..
Scetta, G.; Selles, N.; Heuillet, P.; Ciccotti, M.; Creton, C. Cyclic fatigue failure of TPU using a crack propagation approach. Polym. Test. 2021 , 97 , 107140..
Scetta, G.; Euchler, E.; Ju, J.; Selles, N.; Heuillet, P.; Ciccotti, M.; Creton, C. Self-organization at the crack tip of fatigue-resistant thermoplastic polyurethane elastomers. Macromolecules 2021 , 54 , 8726−8737..
Wang, S.; Tang, S.; He, C.; Wang, Q. Cyclic deformation and fatigue failure mechanisms of thermoplastic polyurethane in high cycle fatigue. Polymers 2023 , 15 , 899..
Lee, J. H.; Lee, H. S.; Kwak, J. B. Mechanical characterization of polymeric thin films using nano cutting method. Int. J. Precis. Eng. Man. 2020 , 21 , 1091−1097..
Ribas, M.; Akhavan-Safar, A.; Carbas, R. J. C.; Marques, E. A. S.; Wenig, S.; da Silva, L. F. M. Mixed mode fatigue crack growth and fatigue threshold analysis in polyurethane adhesives at elevated temperatures. Int. J. Fatigue 2024 , 183 , 108275..
Rodriguez, E. L.; Basar, R.; Kolycheck, E. G.; Tseng, H. S. Fatigue cut growth of thermoplastic polyurethanes. J. Reinf. Plast. Compos. 1994 , 13 , 2−19..
. Robertson, C. G.; Stoček, R.; Mars, W. V., The Fatigue Threshold of Rubber and Its Characterization Using the CuttingMethod. In Fatigue Crack Growth in Rubber Materials: Experiments and Modelling , Heinrich, G., Kipscholl, R., Stoček, R., Eds. Springer International Publishing: Cham, 2021 ; pp. 57−83..
Coleman, M. M.; Lee, K. H.; Skrovanek, D. J.; Painter, P. C. Hydrogen bonding in polymers. 4. Infrared temperature studies of a simple polyurethane. Macromolecules 1986 , 19 , 2149−2157..
. Yılgör, E.; Yılgör, İ.; Yurtsever, E. Hydrogen bonding and polyurethane morphology. I. Quantum mechanical calculations of hydrogen bond energies and vibrational spectroscopy of model compounds Polymer 2002, 43 , 6551-6559..
Painter, P. C.; Park, Y.; Coleman, M. M. Hydrogen bonding in polymer blends. 2. Theory. Macromolecules 1988 , 21 , 66−72..
Chattopadhyay, D. K.; Webster, D. C. Thermal stability and flame retardancy of polyurethanes. Prog. Polym. Sci. 2009 , 34 , 1068−1133..
Krol, P. Synthesis methods, chemical structures and phase structures of linear polyurethanes. Properties and applications of linear polyurethanes in polyurethane elastomers, copolymers and ionomers. Prog. Mater Sci. 2007 , 52 , 915−1015..
Cooper, S. L.; Tobolsky, A. V. Properties of Linear Elastomeric Polyurethanes. J. Appl. Polymer Sci. 1966 , 10 , 1−2..
Zhang, X.; Sun, S.; Ning, N.; Yan, S.; Wu, X.; Lu, Y.; Zhang, L. Visualization and quantification of the microstructure evolution of isoprene rubber during uniaxial stretching using AFM nanomechanical mapping. Macromolecules 2020 , 53 , 3082−3089..
Wang, J.; Wang, M.; Zhang, X.; Han, Y.; Wu, Y.; Wang, D.; Qin, X.; Lu, Y.; Zhang, L. Quantification characterization of hierarchical structure of polyurethane by advanced AFM and X-ray techniques. ACS Appl. Mater. Interfaces 2023 , 15 , 45388−45398..
Tocha, E.; Janik, H.; Debowski, M.; Vancso, G. J. Morphology of polyurethanes revisited by complementary AFM and TEM. J. Macromol. Sci. B 2002 , 41 , 129 1−1304..
Janik, H. Electron-beam irradiation in TEM of hard-segment homopolymers and polyurethanes with different hard-segment content. Macromol. Rapid Commun. 2004 , 25 , 1167−1170..
Briber, R. M.; Thomas, E. L. Investigation of two crystal forms in MDI/BDO-based polyurethanes. J. Macromol. Sci. B 1983 , 22 , 509−528..
Bajsic, E. G.; Rek, V.; Sendijarevic, A.; Sendijarevic, V.; Frisch, K. C. DSC study of morphological changes in segmented polyurethane elastomers. J. Elastom. Plast. 2000 , 32 , 162−182..
Chien, Y. C.; Chuang, W. T.; Jeng, U. S.; Hsu, S. H. Preparation, characterization, and mechanism for biodegradable and biocompatible polyurethane shape memory elastomers. ACS Appl. Mater. Interfaces 2017 , 9 , 5419−5429..
Sánchez-Adsuar, M. S. Influence of the composition on the crystallinity and adhesion properties of thermoplastic polyurethane elastomers. Int. J. Adhes. Adhes. 2000 , 20 , 291−298..
Waletzko, R. S.; Korley, L. T. J.; Pate, B. D.; Thomas, E. L.; Hammond, P. T. Role of increased crystallinity in deformation-induced structure of segmented thermoplastic polyurethane elastomers with PEO and PEO-PPO-PEO soft segments and HDI hard segments. Macromolecules 2009 , 42 , 2041−2053..
Chen, C. P.; Dai, S. A.; Chang, H. L.; Su, W. C.; Wu, T. M.; Jeng, R. J. Polyurethane elastomers through multi-hydrogen-bonded association of dendritic structures. Polymer 2005 , 46 , 11849−11857..
Hergenrother, R. W.; Wabers, H. D.; Cooper, S. L. Effect of hard segment chemistry and strain on the stability of polyurethanes: in vivo biostability. Biomaterials 1993 , 14 , 449−458..
Zhu, P.; Dong, X.; Wang, D. Strain-induced crystallization of segmented copolymers: deviation from the classic deformation mechanism. Macromolecules 2017 , 50 , 3911−3921..
Yeh, F.; Hsiao, B. S.; Sauer, B. B.; Michel, S.; Siesler, H. W. In-situ studies of structure development during deformation of a segmented poly(urethane-urea) elastomer. Macromolecules 2003 , 36 , 1940−1954..
Darren; J.; Martin; Gordon; F.; Meijs; Pathiraja; A.; Gunatillake; Simon. The effect of average soft segment length on morphology and properties of a series of polyurethane elastomers. II. SAXS-DSC annealing study. J. Appl. Polym. Sci. 1997 , 64 , 803−817..
Ren, L.; Shah, P. N.; Faust, R. Morphology and tensile properties of model thermoplastic polyurethanes with MDI/butanediol based monodisperse hard segments. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54 , 2485−2493..
Kim, J.; Zhang, G.; Shi, M.; Suo, Z. Fracture, fatigue, and friction of polymers in which entanglements greatly outnumber cross-links. Science 2021 , 374 , 212−216..
Webber, R. E.; Creton, C.; Brown, H. R.; Gong, J. P. Large strain hysteresis and mullins effect of tough double-network hydrogels. Macromolecules 2007 , 40 , 2919−2927..
Lake, G. J.; Thomas, A. G. The strength of highly elastic materials. J. Math. Phys. 1967 , 300 , 108−119..
Chu, B.; Gao, T.; Li, Y.; Wang, J.; Desper, C. R.; Byrne, C. A. Microphase separation kinetics in segmented polyurethanes: effects of soft segment length and structure. Macromolecules 1992 , 25 , 5724−5729..
Lake, G. J.; Yeoh, O. H. Measurement of rubber cutting resistance in the absence of friction. Int. J. Fracture 1978 , 14 , 509−526..
Lake, G. J.; Lindley, P. B. The mechanical fatigue limit for rubber. J. Appl. Polym. Sci. 1965 , 9 , 1233−1251..
Slootman, J.; Yeh, C. J.; Millereau, P.; Comtet, J.; Creton, C. A molecular interpretation of the toughness of multiple network elastomers at high temperature. Proc. Natl Acad. Sci. U. S. A. 2022 , 119 , e2116127119..
Qiu, W.; Gurr, P. A.; Qiao, G. G. Regulating color activation energy of mechanophore-linked multinetwork elastomers. Macromolecules 2020 , 53 , 4090−4098..
Persson, B. N. J.; Albohr, O.; Heinrich, G.; Ueba , H. Crack propagation in rubber-like materials. J. Phys.-Condens. Mat. 2005 , 17 , R1071..
Matsuda, T.; Nakajima, T.; Fukuda, Y.; Hong, W.; Sakai, T.; Kurokawa, T.; Chung, U. I.; Gong, J. P. Yielding criteria of double network hydrogels. Macromolecules 2016 , 49 , 1865−1872..
0
Views
296
Downloads
0
CSCD
Publicity Resources
Related Articles
Related Author
Related Institution
京公网安备11010802046900号