scholarly journals Dynamic Processes and Mechanisms Involved in Relaxations of Single-Chain Nano-Particle Melts

Polymers ◽  
2021 ◽  
Vol 13 (14) ◽  
pp. 2316
Author(s):  
Jon Maiz ◽  
Ester Verde-Sesto ◽  
Isabel Asenjo-Sanz ◽  
Paula Malo de Molina ◽  
Bernhard Frick ◽  
...  
Keyword(s):  
Nano Particles ◽  
X Ray Diffraction ◽  
Single Chain ◽  
Mechanical Spectroscopy ◽  
Atomic Displacements ◽  
Quasielastic Neutron ◽  
Cross Links ◽  
Quasielastic Neutron Scattering ◽  
Β Relaxation ◽  
The Impact

We present a combined study by quasielastic neutron scattering (QENS), dielectric and mechanical spectroscopy, calorimetry and wide-angle X-ray diffraction on single-chain nano-particles (SCNPs), using the corresponding linear precursor chains as reference, to elucidate the impact of internal bonds involving bulky cross-links on the properties of polymer melts. Internal cross-links do not appreciably alter local properties and fast dynamics. This is the case of the average inter-molecular distances, the β-relaxation and the extent of the atomic displacements at timescales faster than some picoseconds. Contrarily, the α-relaxation is slowed down with respect to the linear precursor, as detected by DSC, dielectric spectroscopy and QENS. QENS has also resolved broader response functions and stronger deviations from Gaussian behavior in the SCNPs melt, hinting at additional heterogeneities. The rheological properties are also clearly affected by internal cross-links. We discuss these results together with those previously reported on the deuterated counterpart samples and on SCNPs obtained through a different synthesis route to discern the effect of the nature of the cross-links on the modification of the diverse properties of the melts.

An extended revision of the interlayer structures of one- and two- layer hydrates of Na- vermiculite

Clay Minerals ◽  
2002 ◽  
Vol 37 (1) ◽  
pp. 157-168 ◽  
Author(s):  
J. Beyer ◽  
H. Graf Von Reichenbach
Keyword(s):  
Rotational Correlation Time ◽  
Silicate Layer ◽  
Water Molecules ◽  
X Ray Diffraction ◽  
Interlayer Water ◽  
Partial Loss ◽  
Stacking Order ◽  
Quasielastic Neutron ◽  
Quasielastic Neutron Scattering ◽  
Water Contents

AbstractThe interlayer structures in one- and two-layer hydrates of Na-vermiculite are described by presenting the positional parameters of their constituent atoms, including protons.The revision of these structures has been accomplished by: (1) determining accurate water contents of the two hydrates by thermoanalysis (TG, DSC); (2) using earlier X-ray diffraction data published by Slade et al.(1985) and de la Calle et al. (1984) as a reference; and (3) applying least-squares refinements when considering the constraints for atomic distances and bond angles between interlayer constituents.In the 1.485 nm hydrate of Na-vermiculite (nH2O/nNa ≈ 4), sharing edges of Na(OH2)6 octahedra cause their chainlike arrangement. The chains are aligned along [100] and are stabilized by H-bonds between interlayer water molecules and oxygens of the silicate layer. The partial loss of these bonds during dehydration forces the stacking order to change from V3 to Vc in the resulting 1.185 nm (nH2O/nNa ≈ 2) hydrate.This new understanding may help to explain differences in the rotational correlation time of water molecules between one- and two-layer hydrates of vermiculite as observed by quasielastic neutron scattering (Swenson et al., 2000).

scholarly journals Collective Motions and Mechanical Response of a Bulk of Single-Chain Nano-Particles Synthesized by Click-Chemistry

Polymers ◽  
2020 ◽  
Vol 13 (1) ◽  
pp. 50
Author(s):  
Jon Maiz ◽  
Ester Verde-Sesto ◽  
Isabel Asenjo-Sanz ◽  
Peter Fouquet ◽  
Lionel Porcar ◽  
...  
Keyword(s):  
Click Chemistry ◽  
Mechanical Response ◽  
Spin Echo ◽  
Density Fluctuations ◽  
Nano Particles ◽  
Neutron Spin ◽  
Single Chain ◽  
Length Scales ◽  
Molecular Reaction ◽  
Cross Links

We investigate the effect of intra-molecular cross-links on the properties of polymer bulks. To do this, we apply a combination of thermal, rheological, diffraction, and neutron spin echo experiments covering the inter-molecular as well as the intermediate length scales to melts of single-chain nano-particles (SCNPs) obtained through ‘click’ chemistry. The comparison with the results obtained in a bulk of the corresponding linear precursor chains (prior to intra-molecular reaction) and in a bulk of SCNPs obtained through azide photodecomposition process shows that internal cross-links do not influence the average inter-molecular distances in the melt, but have a profound impact at intermediate length scales. This manifests in the structure, through the emergence of heterogeneities at nanometric scale, and also in the dynamics, leading to a more complex relaxation behavior including processes that allow relaxation of the internal domains. The influence of the nature of the internal bonds is reflected in the structural relaxation that is slowed down if bulky cross-linking agents are used. We also found that any residual amount of cross-links is critical for the rheological behavior, which can vary from an almost entanglement-free polymer bulk to a gel. The presence of such inter-molecular cross-links additionally hinders the decay of density fluctuations at intermediate length scales.

Symmetry breaking in convergent-beam diffraction

1989 ◽  
Vol 47 ◽  
pp. 480-481
Author(s):  
D.J. Eaglesham
Keyword(s):  
Symmetry Breaking ◽  
Point Group ◽  
X Ray Diffraction ◽  
Multiple Diffraction ◽  
Space Groups ◽  
Atomic Displacements ◽  
Small Probe ◽  
Phase Sensitive ◽  
Convergent Beam

Convergent Beam Electron Diffraction is now almost routinely used in the determination of the point- and space-groups of crystalline samples. In addition to its small-probe capability, CBED is also postulated to be more sensitive than X-ray diffraction in determining crystal symmetries. Multiple diffraction is phase-sensitive, so that the distinction between centro- and non-centro-symmetric space groups should be trivial in CBED: in addition, the stronger scattering of electrons may give a general increase in sensitivity to small atomic displacements. However, the sensitivity of CBED symmetry to the crystal point group has rarely been quantified, and CBED is also subject to symmetry-breaking due to local strains and inhomogeneities. The purpose of this paper is to classify the various types of symmetry-breaking, present calculations of the sensitivity, and illustrate symmetry-breaking by surface strains.CBED symmetry determinations usually proceed by determining the diffraction group along various zone axes, and hence finding the point group. The diffraction group can be found using either the intensity distribution in the discs

A New Polyethylene Corrosion Protecting Coating with Ion Selectivity

2011 ◽  
Vol 314-316 ◽  
pp. 273-278
Author(s):  
Yu Hua Dong ◽  
Ke Ren ◽  
Qiong Zhou
Keyword(s):  
Ion Selectivity ◽  
Nano Particles ◽  
Ammonium Bromide ◽  
Linear Low Density Polyethylene ◽  
X Ray Diffraction ◽  
Sulfosalicylic Acid ◽  
X Ray ◽  
Chemically Modified ◽  
Before And After ◽  
Industrial Standards

Linear low density polyethylene (LLDPE) was chemically modified with grafting maleic anhydride (MAH) monomer on its backbone by melting blending. Nano-particles SiO2 was modified by cationic surfactant hexadecyl trimethyl ammonium bromide (CTAB) and anionic surfactant sulfosalicylic acid (SSA) and added to PE coating respectively. Measurement of membrane potential showed that the coating containing modified SiO2 nano-particles had characteristic of ion selectivity. The properties of the different coatings were investigated according to relative industrial standards. Experimental results indicated that PE coating with ion selectivity had better performances, such as adhesion strength, cathodic disbonding and anti-corrosion, than those of coating without ion selectivity. Crystal structure of the coatings before and after alkali corrosion was characterized by Fourier transform infrared spectra (FTIR) and X-ray diffraction (XRD). Structure of the coating without ion selectivity was damaged by NaOH alkali solution, causing mechanical properties being decreased. And the structure of the ion selective coatings was not affected.

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