Crystallization in Stretched Polymer Networks. I. trans-Polychloroprene

1967 ◽  
Vol 40 (4) ◽  
pp. 1071-1083 ◽  
Author(s):  
A. N. Gent
Keyword(s):  
Melting Temperature ◽  
Polymer Networks ◽  
Crystal Form ◽  
Simple Extension ◽  
Theoretical Treatment ◽  
Nucleation Kinetics ◽  
Segmental Mobility ◽  
Melting Temperatures ◽  
Direct Measurements ◽  
Stress Changes

Abstract Changes in tensile stress afford a simple means of studying the rates of crystallization and the melting temperatures in crosslinked polymers subjected to simple extension. The form and magnitude of the stress changes in networks of trans-polychloroprene are closely similar to those observed for cis-1:4-polyisoprene and cis-l:4-polybutadiene networks. They are in accord with the formation of oriented crystallites and incompatible with folded chain crystallization at extensions as low as 15 per cent. It seems likely that the present networks do not crystallize by chain folding even in the unstretched state. The large increases in rate of crystallization with extension are approximately accounted for by corresponding increases in the equilibrium melting temperature. Direct measurements of the melting temperature show similar rises with extension. The rise in melting temperature is in good agreement with Flory's theoretical treatment of oriented crystallization at extension ratios of three and higher (when the crystallite orientation is complete) for three networks having different degrees of crosslinking. When referred to a constant segmental mobility, namely, that obtaining at Tg+50° C, the rates of crystallization at various extensions obey a common dependence upon the degree of supercooling. This relation is in fair accord with theories of nucleation kinetics, except at the lowest temperatures where there is some indication of the appearance of a new crystal form.

Crystallization in Stretched Polymer Networks. II. trans-Polyisoprene

1967 ◽  
Vol 40 (5) ◽  
pp. 1394-1408
Author(s):  
A. N. Gent
Keyword(s):  
Tensile Stress ◽  
Melting Temperature ◽  
Satisfactory Agreement ◽  
Polymer Networks ◽  
Crystal Forms ◽  
Melting Temperatures ◽  
Test Pieces ◽  
Oriented Crystallization ◽  
Crystal Melting ◽  
Large Contraction

Abstract Measurements are described of the rates of crystallization and crystal melting temperatures in stretched test pieces of trans-polyisoprene, crosslinked to various degrees. The increases in rate with extension are attributed to the corresponding increases in melting temperature and hence degree of supercooling. The rise in the melting temperature of both the α and β crystal forms is found to be in satisfactory agreement with Flory's treatment of oriented crystallization. Changes in tensile stress are also generally in accord with the formation of oriented crystallites. For the more lightly crosslinked materials, a pronounced rise in tensile stress occurred during the later stages of crystallization, at extensions below about 100 per cent. Reasons are given for attributing this phenomenon primarily to the relatively large contraction in volume on crystallization, rather than to the formation of folded-chain crystallites.

Structure Effects and Related Polymer Properties in Polybutadiene. I. Preparation and Characterization

1964 ◽  
Vol 37 (1) ◽  
pp. 169-185 ◽  
Author(s):  
M. Berger ◽  
D. J. Buckley
Keyword(s):  
Melting Temperature ◽  
Transition Probabilities ◽  
Benzene Solution ◽  
Amorphous Polymer ◽  
Crystal Form ◽  
The Other ◽  
Random Copolymers ◽  
Trans Content ◽  
X Ray ◽  
Melting Temperatures

Abstract Stereoregular polybutadienes, of both high trans and high cis contents, were isomerized to provide polymers of varying cis-trans content. These isomerizates were used to study structural effects on physical properties. The isomerizations were carried out under photosensitized conditions in benzene solution at 25° C. The reaction was controlled to deliver polymers over the range 0–95 per cent trans content. This range was selected to provide crystalline and semicrystalline polymers whose structures could be examined in terms of sequencing or blocking by established x-ray techniques. Isomer contents were measured accurately by infrared traces. Isomerizations reached an equilibrium of 77 per cent trans regardless of whether the reaction started with high trans or high cis polybutadienes. Intrinsic viscosity was found to increase regularly with trans content in conformity with the larger size of the trans unit. ηsp/c versus c relations were observed to give a complicated form and this subject was deferred for further study. Crystallinity decreased regularly with reduced trans content as the equilibrium of 77 per cent trans was approached. Continued isomerization at the point of equilibrium produced a completely amorphous polymer. The melting temperatures of the crystalline polymers were studied in detail by x-ray camera and counting techniques. These polymers exhibited two crystal forms. One form was stable up to 60° C and invariant with cis-trans content in the range 80–95 per cent trans. Below 80 per cent trans the melting point of this form decreased with further reduction in trans content. The melting temperature of the other crystal form was dependent on trans content and decreased with decreased trans content until it coincided with the melting temperature of the other form. The distributions of trans and cis units and sequences of them were calculated through construction of matrices of transition probabilities. Copolymer theory was invoked to calculate pseudo reactivity ratios for the trans and cis forms. The melting temperatures of the two crystals were found to follow the predicted curves for random copolymers, although not simultaneously. This behavior is discussed. The crystallinity of the isomerizates of high trans content was found to be similar to block copolymers in spite of the fact that the method of their preparation would require that they be characterized as random. The importance of a crystal transition in this case is stressed along with the general effects due to the amount and type of the noncrystallizable unit.

scholarly journals The surface impedance of superconductors and normal metals at high frequencies III. The relation between impedance and superconducting penetration depth

1947 ◽  
Vol 191 (1026) ◽  
pp. 399-415 ◽  
Keyword(s):  
Magnetic Field ◽  
Penetration Depth ◽  
Surface Impedance ◽  
Simple Extension ◽  
High Frequencies ◽  
Resistivity Measurements ◽  
Direct Measurements ◽  
Normal Metals ◽  
Velocity Of Propagation ◽  
Theory Of Superconductivity

The theory developed in II is extended to cover the case of a superconductor, and a formula is derived relating the r. f. resistivity to the superconducting penetration depth and other parameters of the metal. It is shown how the penetration depth may be deduced directly from measurements of the skin reactance, and a method of measuring reactance is described, based essentially on the variation of the velocity of propagation along a transmission line due to the reactance of the conductors. For technical reasons it is not convenient to measure the reactance absolutely, but a simple extension of the technique described in I enables the change in reactance to be accurately measured when superconductivity is destroyed by a magnetic field. The method has been applied to mercury and tin. In the former case the results are in agreement with Shoenberg’s direct measurements, and confirm that the penetration depth at 0° K is of the order of 7 x 10 –6 cm. The theory developed at the beginning of the paper is used to deduce the variation of penetration depth with temperature from the resistivity measurements of I, and it is shown that agreement with other determinations and with the reactance measurements is fairly good, but not perfect. Some of the assumptions used in developing the theory are critically discussed, and a qualitative account is given to show how Heisenberg’s theory of superconductivity offers an explanation of some of the salient features of superconductivity and inparticular indicates the relation between superconducting and normal electrons.

Impact of dynamic covalent chemistry and precise linker length on crystallization kinetics and morphology in ethylene vitrimers

Soft Matter ◽  
2022 ◽  
Author(s):  
Bhaskar Soman ◽  
Yoo Kyung Go ◽  
Chengtian Shen ◽  
Cecilia Leal ◽  
Christopher M. Evans
Keyword(s):  
Crystal Structure ◽  
Melting Temperature ◽  
Crystallization Kinetics ◽  
Polymer Networks ◽  
Exchange Reactions ◽  
Dynamic Covalent Chemistry ◽  
Linker Length

Vitrimers, dynamic polymer networks with topology conserving exchange reactions, can lead to unusual evolution of the melting temperature and crystal structure of ethylene networks.

Studies on the Melting of DNA

1974 ◽  
Vol 29 (3-4) ◽  
pp. 130-132
Author(s):  
Gokul Chandra Das
Keyword(s):  
Ionic Strength ◽  
Melting Temperature ◽  
Thermal Denaturation ◽  
Spectrophotometric Methods ◽  
Melting Temperatures

Abstract The thermal denaturation of the native DNA in solvents of varying salt concentrations was studied by viscometric and spectrophotometric methods. It was observed that within the molarity range of 0.02 ᴍ to 0.3 ᴍ, the melting temperatures obtained by the two independent methods agreed well, but that at lower ionic strength the agreement was not satisfactory. Both the visco­metric and the spectrophotometric measurements showed an increase of the melting temperature with increasing counterion concentration and a levelling off effect in the neighbourhood of 0.3 ᴍ.

scholarly journals Influence of PCR Reagents on DNA Polymerase Extension Rates Measured on Real-Time PCR Instruments

2014 ◽  
Vol 60 (2) ◽  
pp. 334-340 ◽  
Author(s):  
Jesse L Montgomery ◽  
Carl T Wittwer
Keyword(s):  
Real Time ◽  
Melting Temperature ◽  
Dna Polymerase ◽  
Real Time Pcr ◽  
Monovalent Cation ◽  
Polymerase Activity ◽  
Simple Extension ◽  
Extension Rate ◽  
Nucleotide Analogs ◽  
Dna Dyes

Abstract BACKGROUND Radioactive DNA polymerase activity methods are cumbersome and do not provide initial extension rates. A simple extension rate assay would enable study of basic assumptions about PCR and define the limits of rapid PCR. METHODS A continuous assay that monitors DNA polymerase extension using noncovalent DNA dyes on common real-time PCR instruments was developed. Extension rates were measured in nucleotides per second per molecule of polymerase. To initiate the reaction, a nucleotide analog was heat activated at 95 °C for 5 min, the temperature decreased to 75 °C, and fluorescence monitored until substrate exhaustion in 30–90 min. RESULTS The assay was linear with time for over 40% of the reaction and for polymerase concentrations over a 100-fold range (1–100 pmol/L). Extension rates decreased continuously with increasing monovalent cation concentrations (lithium, sodium, potassium, cesium, and ammonium). Melting-temperature depressors had variable effects. DMSO increased rates up to 33%, whereas glycerol had little effect. Betaine, formamide, and 1,2-propanediol decreased rates with increasing concentrations. Four common noncovalent DNA dyes inhibited polymerase extension. Heat-activated nucleotide analogs were 92% activated after 5 min, and hot start DNA polymerases were 73%–90% activated after 20 min. CONCLUSIONS Simple DNA extension rate assays can be performed on real-time PCR instruments. Activity is decreased by monovalent cations, DNA dyes, and most melting temperature depressors. Rational inclusion of PCR components on the basis of their effects on polymerase extension is likely to be useful in PCR, particularly rapid-cycle or fast PCR.

Analysis of structures and melting properties of the 19-atom Ni–Co clusters

2014 ◽  
Vol 28 (25) ◽  
pp. 1450171 ◽  
Author(s):  
Shi-Wei Ren ◽  
Jing-Wei Sun ◽  
Yan-Zhong Hao
Keyword(s):  
Melting Temperature ◽  
Nickel Atom ◽  
Melting Temperatures ◽  
Pure Cobalt ◽  
Melting Phenomenon ◽  
Nickel Clusters ◽  
Melting Properties ◽  
Mixed Clusters ◽  
Dynamics Method ◽  
Cobalt And Nickel

In this paper, by using the classical molecular dynamics method and the GEAM potential, the geometric structure and the melting properties of the 19-atom Ni – Co clusters with different compositions are studied. It is found that all the clusters have the double icosahedron structures although some of the structures are slightly deformed. With the increase of the temperature, a pre-melting phenomenon is observed. The pre-melting temperatures of the pure cobalt and nickel clusters are very close. But on the whole, the pre-melting temperature decreases with the increase of the number of the nickel atom for the mixed clusters. The effects of the substitution atoms on the melting temperature of the clusters are similar to that on the pre-melting temperature although there are some oscillations in the decrease process. The mechanism of these findings are also investigated and analyzed.

Thermodynamics of Crystallization in High Polymers. Natural Rubber

1955 ◽  
Vol 28 (3) ◽  
pp. 718-727 ◽  
Author(s):  
Donald E. Roberts ◽  
Leo Mandelkern
Keyword(s):  
Natural Rubber ◽  
Melting Temperature ◽  
Low Temperatures ◽  
Rapid Heating ◽  
Heat Of Fusion ◽  
Low Molecular Weight ◽  
Heating Rates ◽  
Equilibrium Melting Temperature ◽  
Clapeyron Equation ◽  
Melting Temperatures

Abstract The existence of an equilibrium melting temperature, T0m, at 28 ± 1°, for unstretched natural rubber has been established, using dilatometric methods. The lower melting temperatures previously observed are a consequence of the low temperatures of crystallization and the rapid heating rates employed. From melting point studies of mixtures of the polymer with low molecular-weight diluents, the heat of fusion per repeating unit, ΔHu has been evaluated as 15.3 ± 0.5 cal./g. The values of ΔHu and T0m have then been combined with data of other workers to obtain the following information concerning natural rubber: (1) The variation of melting temperature with applied hydrostatic pressure has been calculated from the Clapeyron equation to be 0.0465° C/atm. (2) The degree of erystallinity resulting from maintaining a sample at 0° until the rate of crystallization is negligible has been calculated, by three independent methods, to be in the range 26 to 31 per cent. (3) Analysis of the stress-strain-temperature relationship has indicated that crystallization is the cause of the large internal energy changes that are observed at relatively high elongations.

Effect of Al2O3 and CaF2 on Melting Temperature of High Calcium Ladle Desulfurization Slag

2015 ◽  
Vol 1094 ◽  
pp. 325-328
Author(s):  
Wei Fan ◽  
Jin Zhu Zhang ◽  
Wan Zhong Ao ◽  
Jun Huang
Keyword(s):  
Melting Temperature ◽  
Orthogonal Design ◽  
Molten Iron ◽  
Iron And Steel ◽  
Melting Temperatures ◽  
High Calcium ◽  
Analytical Reagent ◽  
The Impact

The external desulphurization of molten iron has become an important step in the production of steel and iron. The melting temperatures of high calcium desulfurization slag, which were taken from Shougang Shuicheng Iron and Steel (Group) Co. Limited, were investigated on basis of the method of hemisphaerium temperature. The contents of CaO, Al2O3 and CaF2 in the slag were adjusted in 47%-53%, 14%-20% and 2%-10% respectively by adding analytical reagent Ca (OH)2, Al2O3 and CaF2 using orthogonal design. The results show that the melting temperature of desulfurization slag decreases obviously with the increase of the content of Al2O3 between 14% and 20%, and decreased markedly with the increase of the content of CaF2 lower than 8%. The impact to the melting temperature of the high calcium slag is as follows: Al2O3 > CaF2 > CaO.

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