Bd. Kaushiva et al., Surfactant level influences on structure and properties of flexible slabstock polyurethane foams, POLYMER, 41(1), 2000, pp. 285-310
A series of flexible polyurethane slabstock foam samples were prepared with
varying surfactant concentration. Several samples were also prepared by qu
enching small pieces into liquid nitrogen during the foaming process. The m
orphology of these materials was characterized at many length scales via sc
anning electron microscopy (SEM), transmission electron microscopy (TEM), w
ide-angle and small-angle X-ray scattering (WAXS and SAXS), tapping-mode at
omic force microscopy (AFM), and Fourier transform infrared spectroscopy (F
TIR). AFM was also utilized to probe trends in the mechanical stiffness of
hard domains in the polyurethane foam. Differential scanning calorimetry (D
SC) and dynamic mechanical analysis (DMA) were applied to examine the therm
al and viscoelastic properties of these foams. It was shown in this study t
hat collapse of the cellular structure of a foam prior to the point of urea
precipitation alters the aggregation behavior of the hard domains and infl
uences their ultimate properties. Samples without surfactant quenched in li
quid nitrogen exhibited urea-rich aggregations on the order of 2-4 mu m wit
h similar sized urea-poor regions. Equivalent samples with surfactant showe
d no such aggregations, suggesting that surfactant does play a principal ro
le in the way that urea precipitates in these materials. DMA and DSC reveal
ed that all samples of any surfactant concentration which spontaneously col
lapsed or were quenched or crushed prior to completely curing had a polyol
glass transition 3-5 degrees higher and somewhat broader than any foam samp
le which maintained its cellular structure until cured. This is interpreted
to mean that the polyol matrix of the collapsed, crushed, or quenched mate
rials is not as pure as the cellular samples, indicating that the presence
of the cellular morphology plays a significant role in the microphase separ
ation behavior of the solid-state at the molecular level. This hypothesis i
s supported by the results of WAXS, FTIR, SAXS, and AFM. The WAXS results d
emonstrate that at no surfactant concentration is the ordering, or hydrogen
bonding, within the hard domains being significantly altered; however, in
the lower range of the concentrations studied here, the FTIR results show t
hat the surfactant level in the formulation does play a significant role on
the amount of bidentate hydrogen bonded hard domains that organize locally
. Further, as shown by SAXS, the surfactant concentration influences the me
an chord length across the hard domains. These changes in structure and dom
ain size distribution lead to the properties investigated via AFM, where th
e relative hardness of the hard domains was noted to initially increase as
the surfactant concentration increases and then levels off above a certain
concentration. The surfactant is thus suggested to play a secondary role in
the development of the hard domains by maintaining the cellular structure
in the foam as the phase separation occurs and at least until the polyureth
ane foam has more fully organized hard segment domains. (C) 1999 Elsevier S
cience Ltd. All rights reserved.