Replicated Banded Spherulite: Microscopic Lamellar-assembly of Poly(L-lactic acid) Crystals in the Poly(oxymethylene) Crystal Framework

Li-Jun Ye; Jie-Qing Shen; Kang-Yuan Xie; Zhi-Xiang Li; Yong-Jin Li

doi:10.1007/s10118-018-2085-z

Your Location：

Home >

Browse articles >

Replicated Banded Spherulite: Microscopic Lamellar-assembly of Poly(L-lactic acid) Crystals in the Poly(oxymethylene) Crystal Framework

ARTICLES | Updated：2021-02-18

- Replicated Banded Spherulite: Microscopic Lamellar-assembly of Poly(L-lactic acid) Crystals in the Poly(oxymethylene) Crystal Framework
- Chinese Journal of Polymer Science Vol. 36, Issue 3, Pages: 385-390(2018)
- Affiliations：
  
  College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036, China
- Author bio：
  
  Yong-Jin Li, E-mail yongjin-li@hznu.edu.cn
- Funds：
- DOI：10.1007/s10118-018-2085-z
  CLC：
- Received：26 September 2017，
  
  Accepted：02 November 2017，
  
  Online First：04 December 2017，
  
  Published：05 March 2018
- Accepted：
Scan QR Code
Li-Jun Ye, Jie-Qing Shen, Kang-Yuan Xie, et al. Replicated Banded Spherulite: Microscopic Lamellar-assembly of Poly(L-lactic acid) Crystals in the Poly(oxymethylene) Crystal Framework[J]. Chinese Journal of Polymer Science, 2018, 36(3): 385-390.
DOI：

Li-Jun Ye, Jie-Qing Shen, Kang-Yuan Xie, et al. Replicated Banded Spherulite: Microscopic Lamellar-assembly of Poly(L-lactic acid) Crystals in the Poly(oxymethylene) Crystal Framework[J]. Chinese Journal of Polymer Science, 2018, 36(3): 385-390. DOI： 10.1007/s10118-018-2085-z.

摘要

Abstract

The morphologies of poly(L-lactic acid) (PLLA) spherulites

when crystallized within the pre-existed poly(oxymethylene) (POM) crystal frameworks

have been investigated. PLLA/POM blend is a melt-miscible crystalline/crystalline blend system. Owing to the lower melting point but much faster crystallization rate than PLLA

POM crystallized first upon cooling from the melt state and then melted first during the subsequent heating process in this blend system. Lamellar assembly of PLLA crystals within the pre-existed POM spherulitic frameworks was directly observed with the polarized light microscopy by selectively melting the POM frameworks. The investigation indicated that PLLA crystals fully replicated the spherulitic morphology and optical birefringence of the POM crystal frameworks

which was independent of

. On the other hand

POM could also duplicate the pre-existed PLLA morphologies. The result obtained provides us a possibility to design the lamellar assembly and crystal structures of polymer crystals in miscible crystalline/crystalline polymer blends.

关键词

Keywords

references

A. G. Shtukenberg , Y. O. Punin , E. Gunn , B. Kahr . Spherulites . Chem. Rev. , 2012 . 112 ( 3 ): 1805 - 1838 . DOI: 10.1021/cr200297f http://doi.org/10.1021/cr200297f .

A. G. Shtukenberg , Y. O. Punin , A. Gujral , B. Kahr . Growth actuated bending and twisting of single crystals . Angew. Chem. Int. Ed. , 2014 . 53 ( 3 ): 672 - 699 . DOI: 10.1002/anie.201301223 http://doi.org/10.1002/anie.201301223 .

B. Crist , J. M. Schultz . Polymer spherulites:a critical review . Prog. Polym. Sci. , 2016 . 56 1 - 63 . DOI: 10.1016/j.progpolymsci.2015.11.006 http://doi.org/10.1016/j.progpolymsci.2015.11.006 .

J. M. Schultz . The crystallization and morphology of melt-miscible polymer blends . Front. Chem. China , 2010 . 5 ( 3 ): 262 - 276 . DOI: 10.1007/s11458-010-0211-8 http://doi.org/10.1007/s11458-010-0211-8 .

Y. Zhang , H. Fang , Z. Wang , M. Tang , Z. Wang . Disclosing the formation of ring-banded spherulites for semicrystalline polymers through the double-layer film method . CrystEng Comm , 2014 . 16 ( 6 ): 1026 - 1037 . DOI: 10.1039/C3CE42083C http://doi.org/10.1039/C3CE42083C .

Z. Wang , L. An , W. Jiang , B. Jiang , X. Wang . Ring-banded spherulite surface structure of poly( ε -caprolactone) in its miscible mixtures with poly(styrene- co -acrylonitrile) . J. Polym. Sci., Part B:Polym. Phys. , 1999 . 37 ( 18 ): 2682 - 2691 . DOI: 10.1002/(ISSN)1099-0488 http://doi.org/10.1002/(ISSN)1099-0488 .

Z. Wang , X. Wang , D. Yu , B. Jiang . The Formation of ring-banded spherulites of poly( ε -caprolactone) in its miscible mixtures with poly(styrene- co -acrylonitrile) . Polymer , 1997 . 38 ( 23 ): 5897 - 5901 . DOI: 10.1016/S0032-3861(97)00225-5 http://doi.org/10.1016/S0032-3861(97)00225-5 .

S. Balijepalli , J. M. Schultz . Modeling of crystallization in a blend containing at least one crystallizable component:an analogy from eutectic systems . Macromolecules , 2006 . 39 ( 21 ): 7407 - 7414 . DOI: 10.1021/ma060097v http://doi.org/10.1021/ma060097v .

E. Blümm , A. J. Owen . Miscibility, crystallization and melting of poly(3-hydroxybutyrate)/poly(L-lactide) blends . Polymer , 1995 . 36 ( 21 ): 4077 - 4081 . DOI: 10.1016/0032-3861(95)90987-D http://doi.org/10.1016/0032-3861(95)90987-D .

S. Hirano , Y. Nishikawa , Y. Terada , T. Ikehara , T. Nishi . Miscibility and crystallization behavior of crystalline/crystalline polymer blends . poly(ester carbonate)/poly(L-lactic acid). Polym. J. , 2002 . 34 ( 2 ): 85 - 88 . https://www.researchgate.net/profile/Toshio_Nishi2/publication/260207524_Miscibility_and_Crystallization_Behavior_of_CrystallineCrystalline_Polymer_Blends_Polyester_carbonatePolyl-lactic_acid/links/53f44d900cf2dd489513c8b6/Miscibility-and-Crystallization-Behavior-of-Crystalline-Crystalline-Polymer-Blends-Polyester-carbonate-Polyl-lactic-acid.pdf https://www.researchgate.net/profile/Toshio_Nishi2/publication/260207524_Miscibility_and_Crystallization_Behavior_of_CrystallineCrystalline_Polymer_Blends_Polyester_carbonatePolyl-lactic_acid/links/53f44d900cf2dd489513c8b6/Miscibility-and-Crystallization-Behavior-of-Crystalline-Crystalline-Polymer-Blends-Polyester-carbonate-Polyl-lactic-acid.pdf , .

T. Ikehara , H. Kimura , Z. B. Qiu . Penetrating spherulitic growth in poly(butylene adipate- co -butylene succinate)/poly(ethylene oxide) blends . Macromolecules , 2005 . 38 ( 12 ): 5104 - 5108 . DOI: 10.1021/ma0502809 http://doi.org/10.1021/ma0502809 .

T. Ikehara , T. Nishi . Interpenetrated spherulites of poly(butylene succinate)/poly(vinylidene chloride- co -vinyl chloride) blends . an optical microscopic study. Polym. J. , 2000 . 32 ( 8 ): 683 - 687 . http://www.refdoc.fr/Detailnotice?cpsidt=18650663 http://www.refdoc.fr/Detailnotice?cpsidt=18650663 , .

T. Ikehara , Y. Nishikawa , T. Nishi . Evidence for the formation of interpenetrated spherulites in poly(butylene succinate- co -butylene carbonate)/poly(L-lactic acid) blends investigated by atomic force microscopy . Polymer , 2003 . 44 ( 21 ): 6657 - 6661 . DOI: 10.1016/S0032-3861(03)00685-2 http://doi.org/10.1016/S0032-3861(03)00685-2 .

J. M. Lu , Z. B. Qiu , W. T. Yang . Effects of blend composition and crystallization temperature on unique crystalline morphologies of miscible poly(ethylene succinate)/poly(ethylene oxide) blends . Macromolecules , 2008 . 41 ( 1 ): 141 - 148 . DOI: 10.1021/ma7020997 http://doi.org/10.1021/ma7020997 .

Z. B. Qiu , T. Ikehara , T. Nishi . Unique morphology of poly(ethylene succinate)/poly(ethylene oxide) blends . Macromolecules , 2002 . 35 ( 22 ): 8251 - 8254 . DOI: 10.1021/ma025599x http://doi.org/10.1021/ma025599x .

J. B. Zeng , Q. Y. Zhu , Y. D. Li , Z. C. Qiu , Y. Z. Wang . Unique crystalline/crystalline polymer blends of poly(ethylene succinate) and poly(p-dioxanone):miscibility and crystallization behaviors . J. Phys. Chem. B , 2010 . 114 ( 46 ): 14827 - 14833 . DOI: 10.1021/jp104709z http://doi.org/10.1021/jp104709z .

M. T. Weng , Z. B. Qiu . A spherulitic morphology study of crystalline/crystalline polymer blends of poly(ethylene succinate- co -9.9 mol% ethylene adipate) and poly(ethylene oxide) . Macromolecules , 2013 . 46 ( 21 ): 8744 - 8747 . DOI: 10.1021/ma4017086 http://doi.org/10.1021/ma4017086 .

T. Ikehara , H. Kurihara , T. Kataoka . Effect of poly(butylene succinate) crystals on spherulitic growth of poly(ethylene oxide) in binary blends of the two substances . J. Polym. Sci., Part B:Polym. Phys. , 2009 . 47 ( 5 ): 539 - 547 . DOI: 10.1002/polb.v47:5 http://doi.org/10.1002/polb.v47:5 .

T. Ikehara , H. Kurihara , Z. B. Qiu , T. Nishi . Study of spherulitic structures by analyzing the spherulitic growth rate of the other component in binary crystalline polymer blends . Macromolecules , 2007 . 40 ( 24 ): 8726 - 8730 . DOI: 10.1021/ma070973k http://doi.org/10.1021/ma070973k .

Z. B. Qiu , C. Z. Yan , J. M. Lu , W. T. Yang . Miscible crystalline/crystalline polymer blends of poly(vinylidene fluoride) and poly(butylene succinate- co -butylene adipate):spherulitic morphologies and crystallization kinetics . Macromolecules , 2007 . 40 ( 14 ): 5047 - 5053 . DOI: 10.1021/ma070255y http://doi.org/10.1021/ma070255y .

H. Wang , Z. Gan , J. M. Schultz , S. Yan . A morphological study of poly(butylene succinate)/poly(butylene adipate) blends with different blend ratios and crystallization processes . Polymer , 2008 . 49 ( 9 ): 2342 - 2353 . DOI: 10.1016/j.polymer.2008.02.050 http://doi.org/10.1016/j.polymer.2008.02.050 .

T. C. Wang , H. H. Li , F. Wang , J. M. Schultz , S. K. Yan . Morphologies and deformation behavior of poly(vinylidene fluoride)/poly(butylene succinate) blends with variety of blend ratios and under different preparation conditions . Polym. Chem. , 2011 . 2 ( 8 ): 1688 - 1698 . DOI: 10.1039/c1py00134e http://doi.org/10.1039/c1py00134e .

T. Wang , H. Li , F. Wang , S. Yan , J. M. Schultz . Confined growth of poly(butylene succinate) in its miscible blends with poly(vinylidene fluoride):morphology and growth kinetics . J. Phys. Chem. B , 2011 . 115 ( 24 ): 7814 - 7822 . DOI: 10.1021/jp203680e http://doi.org/10.1021/jp203680e .

J. Liu , B. J. Jungnickel . Crystallization kinetical and morphological peculiarities in binary crystalline/crystalline polymer blends . J. Polym. Sci., Part B:Polym. Phys. , 2007 . 45 ( 15 ): 1917 - 1931 . DOI: 10.1002/(ISSN)1099-0488 http://doi.org/10.1002/(ISSN)1099-0488 .

M. T. Weng , Z. B. Qiu . Unusual fractional crystallization behavior of novel crystalline/crystalline polymer blends of poly(ethylene suberate) and poly(ethylene oxide) with similar melting points . Macromolecules , 2014 . 47 ( 23 ): 8351 - 8358 . DOI: 10.1021/ma502019x http://doi.org/10.1021/ma502019x .

L. J. Ye , J. S. Qiu , T. Wu , X. C. Shi , Y. J. Li . Banded spherulite templated three-dimensional interpenetrated nanoporous materials . RSC Adv. , 2014 . 4 ( 82 ): 43351 - 43356 . DOI: 10.1039/C4RA06943A http://doi.org/10.1039/C4RA06943A .

L. Ye , X. Shi , C. Ye , Z. Chen , M. Zeng , J. You , Y. Li . Crystallization-modulated nanoporous polymeric materials with hierarchical patterned surfaces and 3d interpenetrated internal channels . ACS Appl. Mater. Interfaces , 2015 . 7 ( 12 ): 6946 - 6954 . DOI: 10.1021/acsami.5b00848 http://doi.org/10.1021/acsami.5b00848 .

L. Ye , C. Ye , K. Xie , X. Shi , J. You , Y. Li . Morphologies and crystallization behaviors in melt-miscible crystalline/crystalline blends with close melting temperatures but different crystallization kinetics . Macromolecules , 2015 . 48 ( 23 ): 8515 - 8525 . DOI: 10.1021/acs.macromol.5b01904 http://doi.org/10.1021/acs.macromol.5b01904 .

J. J. Yang , P. J. Pan , L. Hua , B. Zhu , T. Dong , Y. Inoue . Polymorphic crystallization and phase transition of poly(butylene adipate) in its miscible crystalline/crystalline blend with poly(vinylidene fluoride) . Macromolecules , 2010 . 43 ( 20 ): 8610 - 8618 . DOI: 10.1021/ma1015566 http://doi.org/10.1021/ma1015566 .

Z. B. Qiu , C. Z. Yan , J. M. Lu , W. T. Yang , T. Ikehara , T. Nishi . Various crystalline morphology of poly(butylene succinate- co -butylene adipate) in its miscible blends with poly(vinylidene fluoride) . J. Phys. Chem. B , 2007 . 111 ( 11 ): 2783 - 2789 . DOI: 10.1021/jp067606f http://doi.org/10.1021/jp067606f .

Z. He , Y. Liang , C. C. Han . Confined nucleation and growth of poly(ethylene oxide) on the different crystalline morphology of poly(butylene succinate) from a miscible blend . Macromolecules , 2013 . 46 ( 20 ): 8264 - 8274 . DOI: 10.1021/ma4015214 http://doi.org/10.1021/ma4015214 .

P. Pan , L. Zhao , Y. Inoue . Fractional crystallization kinetics of poly(ethylene oxide) in its blends with poly(butylene succinate):molecular weight effects . Macromol. Mater. Eng. , 2013 . 298 ( 8 ): 919 - 927 . DOI: 10.1002/mame.v298.8 http://doi.org/10.1002/mame.v298.8 .

P. Pan , L. Zhao , J. Yang , Y. Inoue . Fractional crystallization and phase segregation in binary miscible poly(butylene succinate)/poly(ethylene oxide) crystalline blends:effect of crystallization temperature . Macromol. Mater. Eng. , 2013 . 298 ( 2 ): 201 - 209 . DOI: 10.1002/mame.v298.2 http://doi.org/10.1002/mame.v298.2 .

Y. He , B. Zhu , W. H. Kai , Y. Inoue . Nanoscale-confined and fractional crystallization of poly(ethylene oxide) in the interlamellar region of poly(butylene succinate) . Macromolecules , 2004 . 37 ( 9 ): 3337 - 3345 . DOI: 10.1021/ma035886g http://doi.org/10.1021/ma035886g .

Y. He , B. Zhu , W. H. Kai , Y. Inoue . Effects of crystallization condition of poly(butylene succinate) component on the crystallization of poly(ethylene oxide) component in their miscible blends . Macromolecules , 2004 . 37 ( 21 ): 8050 - 8056 . DOI: 10.1021/ma049482f http://doi.org/10.1021/ma049482f .

J. M. Schultz . Self-generated fields and polymer crystallization . Macromolecules , 2012 . 45 ( 16 ): 6299 - 6323 . DOI: 10.1021/ma202476t http://doi.org/10.1021/ma202476t .

E. M. Woo , G. Lugito , J. H. Tsai , A. J. Muller . Hierarchically diminishing chirality effects on lamellar assembly in spherulites comprising chiral polymers . Macromolecules , 2016 . 49 ( 7 ): 2698 - 2708 . DOI: 10.1021/acs.macromol.6b00350 http://doi.org/10.1021/acs.macromol.6b00350 .

J. S. Qiu , C. Y. Xing , X. J. Cao , H. T. Wang , L. Wang , L. P. Zhao , Y. J. Li . Miscibility and double glass transition temperature depression of poly(L-lactic acid) (PLLA)/poly(oxymethylene) (POM) blends . Macromolecules , 2013 . 46 ( 14 ): 5806 - 5814 . DOI: 10.1021/ma401084y http://doi.org/10.1021/ma401084y .

A. Keller . The Spherulitic structure of crystalline polymers . Part I. investigations with the polarizing microscope. J. Polym. Sci. , 1955 . 17 ( 84 ): 291 - 308 . http://onlinelibrary.wiley.com/doi/10.1002/pol.1955.120178414/full#references http://onlinelibrary.wiley.com/doi/10.1002/pol.1955.120178414/full#references , .

J. J. Point . Spiral winding in the spherulites of polyethylene . Bull. Acad. R. Belg. , 1955 . 41 982 - 990 . http://link.aps.org/pdf/10.1103/PhysRevLett.83.2749 http://link.aps.org/pdf/10.1103/PhysRevLett.83.2749 , .

F. J. Padden , H. D. Keith . Spherulitic crystallization in polypropylene . J. Appl. Phys. , 1959 . 30 ( 10 ): 1479 - 1484 . DOI: 10.1063/1.1734985 http://doi.org/10.1063/1.1734985 .

F. P. Price . On extinction patterns of polymer spherulites . J. Polym. Sci. , 1959 . 39 ( 135 ): 139 - 150 . DOI: 10.1002/pol.1959.1203913511 http://doi.org/10.1002/pol.1959.1203913511 .

H. D. Keith , F. J. Padden . A phenomenological theory of spherulitic crystallization . J. Appl. Phys. , 1963 . 34 ( 8 ): 2409 - 2421 . DOI: 10.1063/1.1702757 http://doi.org/10.1063/1.1702757 .

H. D. Keith , F. J. Padden , T. P. Russell . Morphological changes in polyesters and polyamides induced by blending with small concentrations of polymer diluents . Macromolecules , 1989 . 22 ( 2 ): 666 - 675 . DOI: 10.1021/ma00192a027 http://doi.org/10.1021/ma00192a027 .

B. Lotz , S. Z. D. Cheng . A critical assessment of unbalanced surface stresses as the mechanical origin of twisting and scrolling of polymer crystals . Polymer , 2005 . 46 ( 3 ): 577 - 610 . DOI: 10.1016/j.polymer.2004.07.042 http://doi.org/10.1016/j.polymer.2004.07.042 .

K. Okano . Note on the lamellar twist is polymer spherulites . Jpn. J. Appl. Phys. , 1964 . 3 351 - 353 . DOI: 10.1143/JJAP.3.351 http://doi.org/10.1143/JJAP.3.351 .

R. M. Michell , A. J. Müller . Confined crystallization of polymeric materials . Prog. Polym. Sci. , 2016 . 54 - 213 . 54-55, 183-213 https://www.sciencedirect.com/science/article/pii/S0079670015001112 https://www.sciencedirect.com/science/article/pii/S0079670015001112 , .

Views

475

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Synchronously Enhancing Crystallization Ability and Mechanical Properties of the Polylactide Film via Incorporating Stereocomplex Crystallite Fibers

Conformation and Dynamics of a Long Active Polymer Chain Confined in a Circular Cavity

Superior Toughened Biodegradable Poly(L-lactic acid)-based Blends with Enhanced Melt Strength and Excellent Low-temperature Toughness via In situ Reaction Compatibilization

Enhanced Segment Mobility Promotes Stereocomplex Crystallization in Polymer Blends via Elevated Segmental Miscibility

Highly Regio- and trans-Selective Ring-opening Metathesis Polymerization of Chiral Aza-norbornene with a Simple Phenylimido-Tungsten Catalyst

Related Author

Yong Wang

De-Xiang Sun

Zhi-Xuan Zhang

An-Yan Wang

Meng-Bo Luo

Chao Wang

Bin Zhao

Yan-Li Zhou

Related Institution

School of Chemistry, Key Laboratory of Advanced Technologies of Materials (Ministry of Education), Southwest Jiaotong University

Department of Physics, Zhejiang University

Department of Physics, Taizhou University

School of Materials Science and Engineering, Changchun University of Technology

Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

⁰