442 research outputs found
Orienting Ion-Containing Block Copolymers Using AC Electric Field
We consider orientation mechanisms for block copolymers in an electric field.
Theoretical and experimental studies have shown that nonuniformity of the
dielectric constant gives rise to a preferred orientation of the melt with
respect to the applied field. We show that the presence of ions, as found in
anionically prepared copolymers, may increase the alignment effect markedly.
Time-varying (ac) and static (dc) fields are considered within a unified
framework. We find that orientation of block copolymers can in principle be
achieved without a dielectric contrast if there is a mobility contrast. The
presence of ions is especially important at small field frequencies, as is in
most experiments. Unlike the no-ions case, it is found that orienting forces
depend on the polymer chain lengths. The mobile-ions mechanism suggested here
can be used to reduce the magnitude of orienting fields as well as to
discriminate between block copolymers of different lengths.Comment: 8 pages, 2 figure
Phase separation and self-assembly in vitrimers: hierarchical morphology of molten and semi-crystalline polyethylene/dioxaborolane maleimide systems
Vitrimers - a class of polymer networks which are covalently crosslinked and
insoluble like thermosets, but flow when heated like thermoplastics - contain
dynamic links and/or crosslinks that undergo an associative exchange reaction.
These dynamic crosslinks enable vitrimers to have interesting
mechanical/rheological behavior, self-healing, adhesive, and shape memory
properties. We demonstrate that vitrimers can self-assemble into complex meso-
and nanostructures when crosslinks and backbone monomers strongly interact.
Vitrimers featuring polyethylene (PE) as the backbone and dioxaborolane
maleimide as the crosslinkable moiety were studied in both the molten and
semi-crystalline states. We observed that PE vitrimers macroscopically phase
separated into dioxaborolane maleimide rich and poor regions, and characterized
the extent of phase separation by optical transmission measurements. This phase
separation can explain the relatively low insoluble fractions and overall
crystallinities of PE vitrimers. Using synchrotron-sourced small-angle X-ray
scattering (SAXS), we discovered that PE vitrimers and their linear precursors
micro-phase separated into hierarchical nanostructures. Fitting of the SAXS
patterns to a scattering model strongly suggests that the nanostructures -
which persist in both the melt and amorphous fraction of the semi-crystalline
state - may be described as dioxaborolane maleimide rich aggregates packed in a
mass fractal arrangement. These findings of hierarchical meso- and
nanostructures point out that incompatibility effects between network
components and resulting self-assembly must be considered for understanding
behavior and the rational design of vitrimer materials
Control of Gelation and Network Properties of Cationically Copolymerized Mono- and Diglycidyl Ethers
International audienceThe development of low temperature curing systems has become a major objective in thermoset technologies for both environmental and economic reasons. The use of protic and chelating additives have recently been underlined for the control of the cationic ring opening polymerization of epoxies, a curing mode that is very efficient at temperatures close from the ambient but that can easily runaway. In this paper, we propose to use this strategy to control the kinetics of the cationic copolymerization of a diepoxy monomer(diglycidyl ether of bisphenol A, DGEBA) with a monoepoxy monomer(phenyl glycidyl ether, PGE). The purpose of the study is to tune the crosslink density (ν e) in order to control the mechanical properties of the materials. The sol-gel transition was first investigated in details at several frequencies by using the Fourier transform mechanical spectroscopy method (FTMS). We found that the gel time (t gel) and the critical conversion (α gel) can be controlled to a great extent by promoting transfers and complexing cationic species involved in the polymerization mechanism. The FTMS method also gives some insight into the structure of the polymer clusters at the sol-gel transition. The results indicate that the various additives used to control the transition have mostly no influence on the clusters' structure. The properties of the fully-cured networks were then investigated via swelling and dynamic mechanical measurements. Both methods indicate that ν e is strongly influenced by the crosslinker content (DGEBA) bu
Dicarboxylic acid-epoxy vitrimers: Influence of off-stoichiometric acid content on cure reactions and thermo-mechanical properties
International audienc
Orienting Ion-Containing Block Copolymers Using Ac Electric Fields
ABSTRACT: We consider orientation mechanisms for block copolymers in an electric field. Theoretical and experimental studies have shown that nonuniformity of the dielectric constant gives rise to a preferred orientation of the melt with respect to the applied field. We show that the presence of ions, as found in anionically prepared copolymers, may increase the alignment effect markedly. Time-varying (ac) and static (dc) fields are considered within a unified framework. We find that orientation of block copolymers can in principle be achieved without a dielectric contrast if there is a mobility contrast. The presence of ions is especially important at small field frequencies, as is in most experiments. Unlike the no-ions case, it is found that orienting forces depend on the polymer chain lengths. The mobile-ions mechanism suggested here can be used to reduce the magnitude of orienting fields as well as to discriminate between block copolymers of different lengths
The non-centrosymmetric lamellar phase in blends of ABC triblock and ac diblock copolymers
The phase behaviour of blends of ABC triblock and ac diblock copolymers is
examined using self-consistent field theory. Several equilibrium lamellar
structures are observed, depending on the volume fraction of the diblocks,
phi_2, the monomer interactions, and the degrees of polymerization of the
copolymers. For segregations just above the order-disorder transition the
triblocks and diblocks mix together to form centrosymmetric lamellae. As the
segregation is increased the triblocks and diblocks spatially separate either
by macrophase-separating, or by forming a non-centrosymmetric (NCS) phase of
alternating layers of triblock and diblock (...ABCcaABCca...). The NCS phase is
stable over a narrow region near phi_2=0.4. This region is widest near the
critical point on the phase coexistence curve and narrows to terminate at a
triple point at higher segregation. Above the triple point there is two-phase
coexistence between almost pure triblock and diblock phases. The theoretical
phase diagram is consistent with experiments.Comment: 9 pages, 8 figures, submitted to Macromolecule
Human Immunoglobulin M Memory B Cells Controlling Streptococcus pneumoniae Infections Are Generated in the Spleen
Splenectomized and asplenic patients have a high incidence of infections by encapsulated bacteria and do not respond to polysaccharide vaccines. To understand whether the absence of the spleen is associated with a defined B cell defect, we analyzed B cell subsets in the peripheral blood. We found that a population of B cells known as immunoglobulin (Ig)M memory is lacking in patients without spleen. The absence of IgM memory B cells correlates with an impaired immune response to encapsulated bacteria not only in splenectomized patients, but also in individuals with an intact spleen. We show that the physiological and transient predisposition to pneumococcal infections of young children (0–2 yr) is associated with the lack of circulating IgM memory B cells and of serum antipolysaccharide IgM. We also demonstrate that IgM memory B cells are undetectable in a fraction of patients with common variable immunodeficiency, who have recurrent and invasive infections by encapsulated bacteria. IgM memory B cells, therefore, require the spleen for their generation and/or survival and are responsible for the protection against encapsulated bacteria
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