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Title: Ultralow stress, thermally stable cross-linked polymer films of polydivinylbenzene (PDVB)

Journal Article · · Langmuir

Although closely related to polystyrene, poly(divinylbenzene) (PDVB) has found limited utility due to the difficulties associated with its synthesis. As a highly cross-linked polymer, PDVB is infusible and insoluble and thus nearly impossible to shape into films by either melt or solvent-based processes. Here, we report the initiated chemical vapor deposition (iCVD) of nearly stress-free, highly transparent, free-standing films of PDVB up to 25 μm thick. Films initially grow under tensile intrinsic stress but become more compressive with thickness and eventually converge to zero-stress values once they reach ≥10 μm in thickness. Upon initial heating, the evaporative loss of unreacted monomer left in the polymer matrix induces between 35 and 45 MPa of tensile stress in the films. Afterward, subsequent heating cycles induce reversible stress and film expansion behaviors. We estimate the degree of cross-linking to be 44%, resulting in high thermal stability (up to 300 °C) and mechanical stiffness (Young’s modulus of 5.2 GPa). As a result, the low stress combined with high cross-linking makes iCVD PDVB an excellent candidate for protective coatings in harsh environments.

Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC52-07NA27344
OSTI ID:
1364741
Report Number(s):
LLNL-JRNL-710659
Journal Information:
Langmuir, Vol. 33, Issue 21; ISSN 0743-7463
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

References (36)

Designing polymer surfaces via vapor deposition journal May 2010
Thin Polymer Films with High Step Coverage in Microtrenches by Initiated CVD journal September 2008
Controllable Cross-Linking of Vapor-Deposited Polymer Thin Films and Impact on Material Properties journal February 2013
Structure and Thermal Properties of Thin Film Poly(α-methylstyrene) Deposited via Plasma-Enhanced Chemical Vapor Deposition journal March 2003
Deposition conditions influence the postdeposition oxidation of methyl methacrylate plasma polymer films journal April 1998
A multi-technique study of the spontaneous oxidation of N-hexane plasma polymers journal June 1994
Photo-oxidation of polymer-like amorphous hydrogenated carbon under visible light illumination journal December 2015
Initiated Chemical Vapor Deposition (iCVD) of Poly(alkyl acrylates):  A Kinetic Model journal May 2006
Synthesis of monodisperse poly(divinylbenzene) microspheres journal December 1993
Thermal stability of polydivinylbenzene and of copolymers of styrene with divinylbenzene and with trivinylbenzene journal May 1961
Polymerization of organic compounds in an electrodeless glow discharge. X. Internal stress in plasma polymers journal November 1977
Stress in thermally annealed parylene films journal October 1992
Photo-oxidation of Polymers Synthesized by Plasma and Initiated CVD  journal November 2015
Mechanisms inducing compressive stress during electrodeposition of Ni journal January 2005
Potential of Hexyl Acrylate Monomer as an Initiator in Photo-initiated CVD: Potential of Hexyl Acrylate Monomer as an Initiator journal November 2013
Refractive index of air: new equations for the visible and near infrared journal January 1996
The Tension of Metallic Films Deposited by Electrolysis journal May 1909
Evolution of coherent islands in Si 1 x Ge x / Si ( 001 ) journal January 1999
The dynamic competition between stress generation and relaxation mechanisms during coalescence of Volmer–Weber thin films journal May 2001
Depth-sensing indentation of low-density brittle nanoporous solids journal July 2009
An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments journal June 1992
Carbon-Hydrogen Stretching Frequencies journal February 1960
Identification of defects and impurities in chemical‐vapor‐deposited diamond through infrared spectroscopy journal August 1994
The preparation and characteristics of poly(divinylbenzene-co-ethylvinylbenzene), including Ambeflite XAD-4. Styrenic resins with pendant vinylbenzene groups journal February 1998
Interaction between Radicals Derived from Two Di-t-Alkyl Peroxides with Some Monomers and Polymers journal May 1999
Transition between kinetic and mass transfer regimes in the initiated chemical vapor deposition from ethylene glycol diacrylate journal September 2009
Mechanical properties of thin films journal November 1989
Origins of Growth Stresses in Amorphous Semiconductor Thin Films journal August 2003
Recommended Values for the Thermal Expansivity of Silicon from 0 to 1000 K journal April 1983
Residual stresses in amorphous alumina films synthesized by ion beam assisted deposition journal April 1995
Thermomechanical Properties of Parylene X, A Room-Temperature Chemical Vapor Depositable Crosslinkable Polymer journal January 2007
Growth of patterned island arrays to identify origins of thin film stress journal March 2014
Measurements of the intrinsic stress in thin metal films journal January 1990
Stress evolution during growth of 1-D island arrays: Kinetics and length scaling journal March 2015
Structural origins of intrinsic stress in amorphous silicon thin films journal February 2012
The thermal properties of porous polydivinylbenzene beads journal January 2002

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