skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties

Abstract

Crystal orientation in semi-crystalline polymers tends to enhance their performance, such as increased yield strength and modulus, along the orientation direction. Zone annealing (ZA) orients the crystal lamellae through a sharp temperature gradient that effectively directs the crystal growth, but the sweep rate (VZA) of this gradient significantly impacts the extent of crystal orientation. Here in this work, we demonstrate rotational zone annealing (RZA) as an efficient method to elucidate the influence of VZA on the crystal morphology of thin films in a single experiment using isotactic poly(1-butene), PB-1, as a model semi-crystalline polymer. These RZA results are confirmed using standard, serial linear ZA to tune the structure from an almost unidirectional oriented morphology to weakly oriented spherulites. The overall crystallinity is only modestly changed in comparison to isothermal crystallization (maximum of 55% from ZA vs. 48% for isothermal crystallization). However, the average grain size increases and the spherulites become anisotropic from ZA. Due to these structural changes, the Young's modulus of the oriented films, both parallel and perpendicular to the spherulite orientation direction, is significantly increased by ZA. The modulus does become anisotropic after ZA due to the directionality in the crystal structure, with more than a threefold increasemore » in the modulus parallel to the orientation direction for the highest oriented film in comparison to the modulus from isothermal crystallization. Lastly, RZA enables rapid identification of conditions to maximize orientation of crystals in thin polymer films, which could find utility in determining conditions to improve crystallinity and performance in organic electronics.« less

Authors:
 [1]; ORCiD logo [1];  [2];  [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [3]; ORCiD logo [1]
  1. Univ. of Akron, OH (United States). Department of Polymer Engineering
  2. Univ. of Akron, OH (United States). Department of Polymer Science
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1430874
Report Number(s):
BNL-203428-2018-JAAM
Journal ID: ISSN 1744-683X; SMOABF
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Soft Matter
Additional Journal Information:
Journal Volume: 13; Journal Issue: 39; Journal ID: ISSN 1744-683X
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Ye, Changhuai, Wang, Chao, Wang, Jing, Wiener, Clinton G., Xia, Xuhui, Cheng, Stephen Z. D., Li, Ruipeng, Yager, Kevin G., Fukuto, Masafumi, and Vogt, Bryan D. Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties. United States: N. p., 2017. Web. doi:10.1039/C7SM01366C.
Ye, Changhuai, Wang, Chao, Wang, Jing, Wiener, Clinton G., Xia, Xuhui, Cheng, Stephen Z. D., Li, Ruipeng, Yager, Kevin G., Fukuto, Masafumi, & Vogt, Bryan D. Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties. United States. doi:10.1039/C7SM01366C.
Ye, Changhuai, Wang, Chao, Wang, Jing, Wiener, Clinton G., Xia, Xuhui, Cheng, Stephen Z. D., Li, Ruipeng, Yager, Kevin G., Fukuto, Masafumi, and Vogt, Bryan D. Thu . "Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties". United States. doi:10.1039/C7SM01366C. https://www.osti.gov/servlets/purl/1430874.
@article{osti_1430874,
title = {Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties},
author = {Ye, Changhuai and Wang, Chao and Wang, Jing and Wiener, Clinton G. and Xia, Xuhui and Cheng, Stephen Z. D. and Li, Ruipeng and Yager, Kevin G. and Fukuto, Masafumi and Vogt, Bryan D.},
abstractNote = {Crystal orientation in semi-crystalline polymers tends to enhance their performance, such as increased yield strength and modulus, along the orientation direction. Zone annealing (ZA) orients the crystal lamellae through a sharp temperature gradient that effectively directs the crystal growth, but the sweep rate (VZA) of this gradient significantly impacts the extent of crystal orientation. Here in this work, we demonstrate rotational zone annealing (RZA) as an efficient method to elucidate the influence of VZA on the crystal morphology of thin films in a single experiment using isotactic poly(1-butene), PB-1, as a model semi-crystalline polymer. These RZA results are confirmed using standard, serial linear ZA to tune the structure from an almost unidirectional oriented morphology to weakly oriented spherulites. The overall crystallinity is only modestly changed in comparison to isothermal crystallization (maximum of 55% from ZA vs. 48% for isothermal crystallization). However, the average grain size increases and the spherulites become anisotropic from ZA. Due to these structural changes, the Young's modulus of the oriented films, both parallel and perpendicular to the spherulite orientation direction, is significantly increased by ZA. The modulus does become anisotropic after ZA due to the directionality in the crystal structure, with more than a threefold increase in the modulus parallel to the orientation direction for the highest oriented film in comparison to the modulus from isothermal crystallization. Lastly, RZA enables rapid identification of conditions to maximize orientation of crystals in thin polymer films, which could find utility in determining conditions to improve crystallinity and performance in organic electronics.},
doi = {10.1039/C7SM01366C},
journal = {Soft Matter},
number = 39,
volume = 13,
place = {United States},
year = {2017},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Crystallization of tethered polyethylene in confined geometries
journal, August 1999


Contact-induced crystallinity for high-performance soluble acene-based transistors and circuits
journal, February 2008

  • Gundlach, D. J.; Royer, J. E.; Park, S. K.
  • Nature Materials, Vol. 7, Issue 3, p. 216-221
  • DOI: 10.1038/nmat2122

Crystallization and Transformation of Polybutene‐1
journal, January 2004

  • Kaszonyiova, M.; Rybnikar, F.; Geil, P. H.
  • Journal of Macromolecular Science, Part B, Vol. 43, Issue 5
  • DOI: 10.1081/MB-200033322

Polymorphic Behavior and Mechanical Properties of Isotactic 1-Butene–Ethylene Copolymers from Metallocene Catalysts
journal, June 2014

  • De Rosa, Claudio; Ruiz de Ballesteros, Odda; Auriemma, Finizia
  • Macromolecules, Vol. 47, Issue 13
  • DOI: 10.1021/ma500088a

High pressure dilatometry on polybutene-1
journal, April 1983

  • Leute, U.; Dollhopf, W.
  • Colloid and Polymer Science, Vol. 261, Issue 4
  • DOI: 10.1007/BF01413935

Preparation of ultra-high modulus polyethylene films by the zone-annealing method
journal, May 1988


Direct Formation of Isotactic Poly(1-butene) Form I Crystal from Memorized Ordered Melt
journal, September 2013

  • Su, Fengmei; Li, Xiangyang; Zhou, Weiming
  • Macromolecules, Vol. 46, Issue 18
  • DOI: 10.1021/ma400952r

Stretching Temperature Dependency of Lamellar Thickness in Stress-Induced Localized Melting and Recrystallized Polybutene-1
journal, September 2013

  • Wang, Yaotao; Jiang, Zhiyong; Fu, Lianlian
  • Macromolecules, Vol. 46, Issue 19
  • DOI: 10.1021/ma401326g

Olefin polymer technologies—History and recent progress at The Dow Chemical Company
journal, August 2008


Kinetics of crystallization in semicrystalline/amorphous polymer mixtures
journal, July 1986


Crystallization Properties and Polymorphic Behavior of Isotactic Poly(1-Butene) from Metallocene Catalysts: The Crystallization of Form I from the Melt
journal, November 2009

  • De Rosa, Claudio; Auriemma, Finizia; Ruiz de Ballesteros, Odda
  • Macromolecules, Vol. 42, Issue 21
  • DOI: 10.1021/ma901453x

Controlling Nucleation and Crystallization in Solution-Processed Organic Semiconductors for Thin-Film Transistors
journal, September 2009

  • Lee, Stephanie S.; Kim, Chang Su; Gomez, Enrique D.
  • Advanced Materials, Vol. 21, Issue 35
  • DOI: 10.1002/adma.200900705

Ultra-high-modulus linear polyethylene through controlled molecular weight and drawing
journal, March 1975


Generating thickness gradients of thin polymer films via flow coating
journal, February 2006

  • Stafford, Christopher M.; Roskov, Kristen E.; Epps, Thomas H.
  • Review of Scientific Instruments, Vol. 77, Issue 2
  • DOI: 10.1063/1.2173072

Controlled Directional Crystallization of Oligothiophenes Using Zone Annealing of Preseeded Thin Films
journal, October 2015

  • Ye, Changhuai; Zhang, Lei; Fu, Guopeng
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 41
  • DOI: 10.1021/acsami.5b06344

Double-Network Hydrogels with Extremely High Mechanical Strength
journal, July 2003


Increased photo- and electroluminescence by zone annealing of spin-coated and vacuum-sublimed amorphous films producing crystalline thin films
journal, December 2003

  • Liu, Chong-Yang; Bard, Allen J.
  • Applied Physics Letters, Vol. 83, Issue 26
  • DOI: 10.1063/1.1636823

Growth Rate of Isotactic Polystyrene Crystals in Thin Films
journal, October 1998

  • Sawamura, Sinzo; Miyaji, Hideki; Izumi, Kunihide
  • Journal of the Physical Society of Japan, Vol. 67, Issue 10
  • DOI: 10.1143/JPSJ.67.3338

Tensile Deformation of Polybutene-1 with Stable Form I at Elevated Temperature
journal, December 2012

  • Wang, Yaotao; Jiang, Zhiyong; Wu, Zhonghua
  • Macromolecules, Vol. 46, Issue 2
  • DOI: 10.1021/ma302389j

Correlating Stiffness, Ductility, and Morphology of Polymer:Fullerene Films for Solar Cell Applications
journal, November 2012

  • Awartani, Omar; Lemanski, Bethany I.; Ro, Hyun Wook
  • Advanced Energy Materials, Vol. 3, Issue 3
  • DOI: 10.1002/aenm.201200595

Preparation of high-modulus and high-strength poly(ethylene terephthalate) fiber by zone annealing
journal, January 1981

  • Kunugi, Toshio; Suzuki, Akihiro; Hashimoto, Minoru
  • Journal of Applied Polymer Science, Vol. 26, Issue 1
  • DOI: 10.1002/app.1981.070260120

Novel Developed Systems and Techniques Based on Double-Network Principle
journal, December 2011

  • Wu, Zi Liang; Kurokawa, Takayuki; Gong, Jian Ping
  • Bulletin of the Chemical Society of Japan, Vol. 84, Issue 12
  • DOI: 10.1246/bcsj.20110201

Variations in Semiconducting Polymer Microstructure and Hole Mobility with Spin-Coating Speed
journal, November 2005

  • DeLongchamp, Dean M.; Vogel, Brandon M.; Jung, Youngsuk
  • Chemistry of Materials, Vol. 17, Issue 23
  • DOI: 10.1021/cm0513637

Orientational Order in Block Copolymer Films Zone Annealed below the Order−Disorder Transition Temperature
journal, September 2007

  • Berry, Brian C.; Bosse, August W.; Douglas, Jack F.
  • Nano Letters, Vol. 7, Issue 9
  • DOI: 10.1021/nl071354s

Preparation of high-modulus and high-strength isotactic polypropylene fiber by zone-annealing method
journal, January 1983

  • Kunugi, Toshio; Ito, Taihei; Hashimoto, Minoru
  • Journal of Applied Polymer Science, Vol. 28, Issue 1
  • DOI: 10.1002/app.1983.070280115

Relationship between Morphology and Deformation Mechanisms of Polyolefins. II
journal, November 1964

  • Sasaguri, K.; Yamada, R.; Stein, R. S.
  • Journal of Applied Physics, Vol. 35, Issue 11
  • DOI: 10.1063/1.1713198

Deformation-induced crystal–crystal transition of polybutene-1: an in situ FTIR imaging study
journal, March 2013


Morphology of Form I′ crystals of polybutene-1 formed on melt-crystallization
journal, April 2015


The Anisotropy of Young's Modulus in Drawn Polyethylene
journal, May 1961


Melt spinning and drawing of 2-methyl-1,3-propanediol-substituted poly(ethylene terephthalate)
journal, June 2003

  • Suh, Jaein; Spruiell, J. E.; Schwartz, Steven A.
  • Journal of Applied Polymer Science, Vol. 88, Issue 11
  • DOI: 10.1002/app.11871

Crystallization kinetics and crystal morphology in thin poly(ethylene oxide) films
journal, June 2003

  • Massa, M. V.; Dalnoki-Veress, K.; Forrest, J. A.
  • The European Physical Journal E - Soft Matter, Vol. 11, Issue 2
  • DOI: 10.1140/epje/i2002-10155-4

Elastic moduli of highly oriented polyoxymethylene
journal, November 1983

  • Choy, C. L.; Leung, W. P.; Huang, C. W.
  • Polymer Engineering and Science, Vol. 23, Issue 16
  • DOI: 10.1002/pen.760231610

Extending Dynamic Range of Block Copolymer Ordering with Rotational Cold Zone Annealing (RCZA) and Ionic Liquids
journal, October 2015


Crystallization of poly(ether ether ketone) oriented by solid-state extrusion
journal, June 1991


Impact of Nanostructure on Mechanical Properties of Norbornene-based Block Copolymers under Simulated Operating Conditions for Biobutanol Membranes
journal, May 2015

  • Ye, Changhuai; Takigawa, Tamami; Burtovvy, Oleksandr (Sasha)
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 22
  • DOI: 10.1021/acsami.5b02692

Anisotropic Elastic Modulus of Oriented Regioregular Poly(3-hexylthiophene) Films
journal, December 2015


Tuning Molecular Relaxation for Vertical Orientation in Cylindrical Block Copolymer Films via Sharp Dynamic Zone Annealing
journal, August 2012

  • Singh, Gurpreet; Yager, Kevin G.; Smilgies, Detlef-M.
  • Macromolecules, Vol. 45, Issue 17
  • DOI: 10.1021/ma301004j

Stretch-Induced Crystal–Crystal Transition of Polybutene-1: An in Situ Synchrotron Radiation Wide-Angle X-ray Scattering Study
journal, March 2012

  • Liu, Yanping; Cui, Kunpeng; Tian, Nan
  • Macromolecules, Vol. 45, Issue 6
  • DOI: 10.1021/ma2026513

Unusual phase behavior in mixtures of poly(ethylene oxide) and ethyl alcohol
journal, January 2005

  • Ho, Derek L.; Hammouda, Boualem; Kline, Steven R.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 44, Issue 3
  • DOI: 10.1002/polb.20726

Effect of Crystallinity and Spherulite Structure on the Mechanical Properties of Poly(1-butene)
journal, September 2009


Effect of tensile strain rate and elongation on crystalline structure and piezoelectric properties of PVDF thin films
journal, February 2007


Synergism on tensile properties of injection molded polybutene-1 /polypropylene blends
journal, June 1993

  • Lee, Mao-Song; Chen, Show-An
  • Polymer Engineering and Science, Vol. 33, Issue 11
  • DOI: 10.1002/pen.760331105

Facile control of long range orientation in mesoporous carbon films with thermal zone annealing velocity
journal, January 2013

  • Xue, Jiachen; Singh, Gurpreet; Qiang, Zhe
  • Nanoscale, Vol. 5, Issue 24
  • DOI: 10.1039/c3nr03591c

Crystal-crystal transformations in isotactic polybutene-1 oriented filaments and in thick molded rods
journal, June 2001

  • Choi, Cheol-Ho; White, James L.
  • Polymer Engineering & Science, Vol. 41, Issue 6
  • DOI: 10.1002/pen.10792

Structure development during melt spinning of linear polyethylene fibers
journal, April 1974


Isotactic poly(butene-1) trigonal crystal growth in the melt
journal, January 2007

  • Yamashita, Motoi; Hoshino, Akitaka; Kato, Minoru
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 45, Issue 6
  • DOI: 10.1002/polb.21052

The Morphology of Directionally Solidified Poly(ethylene oxide) Spherulites
journal, March 1976


Toward Single Crystal Thin Films of Terthiophene by Directional Crystallization Using a Thermal Gradient
journal, August 2011

  • Schweicher, Guillaume; Paquay, Nicolas; Amato, Claire
  • Crystal Growth & Design, Vol. 11, Issue 8
  • DOI: 10.1021/cg2007793

On the molecular mechanism of the crystal transformation (tetragonal-hexagonal) in polybutene-1
journal, May 1982

  • Gohil, R. M.; Miles, M. J.; Petermann, J.
  • Journal of Macromolecular Science, Part B, Vol. 21, Issue 2
  • DOI: 10.1080/00222348208204934

Anisotropic Mechanical Properties of Aligned Polystyrene- block -polydimethylsiloxane Thin Films
journal, October 2013

  • Ye, Changhuai; Singh, Gurpreet; Wadley, Maurice L.
  • Macromolecules, Vol. 46, Issue 21
  • DOI: 10.1021/ma401780r

Structure in Thin and Ultrathin Spin-Cast Polymer Films
journal, August 1996


Solution-Processable α,ω-Distyryl Oligothiophene Semiconductors with Enhanced Environmental Stability
journal, May 2009

  • Mauldin, Clayton E.; Puntambekar, Kanan; Murphy, Amanda R.
  • Chemistry of Materials, Vol. 21, Issue 9
  • DOI: 10.1021/cm900267v

Mechanical relaxation in polypropylene as a function of polymorphism and degree of lamella orientation
journal, February 1969


Effect of annealing temperature on phase composition and tensile properties in isotactic poly(1-butene)
journal, November 2011

  • Chvátalová, Lenka; Beníček, Lubomír; Berková, Kristýna
  • Journal of Applied Polymer Science, Vol. 124, Issue 4
  • DOI: 10.1002/app.35360

High speed melt spinning of poly(L-lactic acid) filaments
journal, April 1998


Morphology and mechanical properties of blown films of a low-density polyethylene/linear low-density polyethylene blend
journal, February 2002

  • Lu, Jianjun; Sue, Hung-Jue
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 40, Issue 6
  • DOI: 10.1002/polb.10115

Directing the film structure of organic semiconductors via post-deposition processing for transistor and solar cell applications
journal, January 2014

  • Hiszpanski, Anna M.; Loo, Yueh-Lin
  • Energy Environ. Sci., Vol. 7, Issue 2
  • DOI: 10.1039/C3EE42615G

Rheology and Morphology of Pristine Graphene/Polyacrylamide Gels
journal, August 2013

  • Das, Sriya; Irin, Fahmida; Ma, Lan
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 17
  • DOI: 10.1021/am402185r

Spatiotemporal growth of faceted and curved single crystals
journal, April 2000


Unidirectional self-assembly of soft templated mesoporous carbons by zone annealing
journal, January 2013

  • Xue, Jiachen; Singh, Gurpreet; Qiang, Zhe
  • Nanoscale, Vol. 5, Issue 17
  • DOI: 10.1039/c3nr02821f

In situ observation of the spherulite deformation in polybutene-1 (Modification I)
journal, November 1980

  • Weynant, E.; Haudin, J. M.; G'Sell, C.
  • Journal of Materials Science, Vol. 15, Issue 11
  • DOI: 10.1007/BF00550534

A buckling-based metrology for measuring the elastic moduli of polymeric thin films
journal, July 2004

  • Stafford, Christopher M.; Harrison, Christopher; Beers, Kathryn L.
  • Nature Materials, Vol. 3, Issue 8, p. 545-550
  • DOI: 10.1038/nmat1175