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.

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.

Nature of Stark Rubber

1955 ◽  
Vol 28 (4) ◽  
pp. 1007-1020 ◽  
Author(s):  
Donald E. Roberts ◽  
Leo Mandelkern
Keyword(s):  
Natural Rubber ◽  
Melting Temperature ◽  
Melting Behavior ◽  
X Ray Diffraction ◽  
Equilibrium Melting Temperature ◽  
X Ray ◽  
Melting Temperatures ◽  
Controlled Conditions ◽  
Previous Assignment ◽  
Diffraction Patterns

Abstract The melting behavior and x-ray diffraction patterns of four different samples of stark rubber have been investigated. The melting temperatures, 39° to 45.5° C, are substantially higher than that observed for natural rubber crystallized by cooling. The x-ray diffraction patterns indicate that the crystallites in stark rubber are oriented. This observation can explain the higher melting temperatures. Thus, the previous assignment of an equilibrium melting temperature, 28° (±1°) C, to unoriented crystalline natural rubber is shown to be appropriate. Several different methods that have been used successfully in preparing stark rubber under controlled conditions in the laboratory are outlined.

Recrystallization and Melting of Partially Melted Stark Rubber

1969 ◽  
Vol 42 (2) ◽  
pp. 540-546
Author(s):  
Donald E. Roberts
Keyword(s):  
Heating Rate ◽  
Melting Temperature ◽  
Specific Volume ◽  
The Other ◽  
Melting Range ◽  
Melting Temperatures ◽  
Slow Decrease

Abstract Two specimens from a piece of stark rubber which had a melting temperature originally at 41° C were partially melted at 38° C and allowed to stand for 11 years, one at about 25° C, the other at 38° C. The first showed a continuous slow decrease in specific volume, while the second increased slowly in volume for 5 months and remained constant for about 5 months more before showing the continuous slow decrease. The melting temperature of the first increased to 45° C and the melting range was broadened. The melting temperature of the second became 52° C and the range was narrowed. Perfecting or enlarging of crystals and the effect of higher recrystallization temperatures have influenced the melting temperatures. The effect of heating rate is discussed in connection with slow increases in volume, attributed to relaxation of oriented regions, during melting.

scholarly journals Chlorinated Water Induced Aging of Pipe Grade Polypropylene Random Copolymers

Polymers ◽  
2019 ◽  
Vol 11 (6) ◽  
pp. 996 ◽  
Author(s):  
Joerg Fischer ◽  
Paul Freudenthaler ◽  
Reinhold Lang ◽  
Wolfgang Buchberger ◽  
Susan Mantell
Keyword(s):  
Fatigue Crack ◽  
Potable Water ◽  
Crystal Form ◽  
Hot Water ◽  
The Other ◽  
Random Copolymers ◽  
Waterborne Diseases ◽  
Water Pipes ◽  
Round Bar ◽  
Effect Of Chlorine

Polypropylene random copolymers (PP-R) are common materials for pressurized hot water pipes. In many pipe systems, potable water is disinfected by chlorine to prevent waterborne diseases. This paper deals with hot chlorinated water induced aging of two PP-R grades with varying morphology. One material had a conventional monoclinic α crystal form (PP-Rα), whereas the other was explicitly beta-nucleated resulting in a trigonal β crystal form with a fine spherulite structure (PP-Rβ). Micro-sized specimens with a thickness of 100 µm were used for aging experiments at 60 °C in chlorinated water with 5 mg/L free chlorine, and aging indicators were monitored for exposure times of up to 2000 h. On the other hand, superimposed mechanical-environmental tests were carried out by using cracked round bar specimens with a diameter of 14 mm to determine the fatigue crack growth (FCG) resistance of both PP-R grades at 60 °C in non-chlorinated and chlorinated water. PP-Rβ was found to outperform PP-Rα with an about 30% higher time-to-embrittlement value of 2000 h. Furthermore, PP-Rβ exhibited an enhanced FCG resistance in both non-chlorinated and chlorinated water. The effect of chlorine content on the deterioration of the FCG resistances was significantly more pronounced for PP-Rα.

The Effect of Fluorine on the Viscosity and Crystallization of Lithium Aluminosilicate Glasses

2012 ◽  
Vol 509 ◽  
pp. 346-352
Author(s):  
Wei Hong Zheng ◽  
Yang Dai ◽  
Mo Zhou Lin ◽  
Kun Yang ◽  
Hao Wu
Keyword(s):  
Melting Temperature ◽  
Glass Ceramics ◽  
Fluorine Content ◽  
X Ray Diffraction ◽  
Lithium Aluminosilicate ◽  
X Ray ◽  
Melting Temperatures ◽  
Aluminosilicate Glasses ◽  
Main Crystalline Phase ◽  
Rotation Viscometer

Lithium aluminosilicate glasses have high viscosities, resulting in high melting temperatures and processing temperatures. In this study, F was added to the LAS glasses to reduce the melting temperature and viscosity for float process. The effects of fluorine content on the viscosity and crystallization of the parent glasses were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), differential thermal analysis (DTA) and rotation viscometer. It was found that the addition of F was useful in reducing the melting temperature and viscosity. The main crystalline phase of resulting glass-ceramics was β-spodumene. The activation energy (E) of LAS glasses was decreased from 460.3 KJ/mol to 417.7 KJ/mol with the addition of 2.63 wt% F, which accelerated the crystallization and enhanced the crystallinity of specimens.

Phase Transition and Thermal Expansion of Ba3RB3O9 (R = Sm–Yb, and Y)

2017 ◽  
Vol 36 (8) ◽  
pp. 763-769 ◽  
Author(s):  
Rayko Simura ◽  
Shohei Kawai ◽  
Kazumasa Sugiyama
Keyword(s):  
Phase Transition ◽  
Thermal Expansion ◽  
High Temperature ◽  
Thermal Expansion Coefficient ◽  
Room Temperature ◽  
The Other ◽  
X Ray Diffraction ◽  
X Ray ◽  
Melting Temperatures ◽  
Type Phase

AbstractHigh temperature powder X-ray diffraction measurements of Ba3RB3O9 (R=Sm–Yb, and Y) were carried out at temperatures ranging from room temperature to just below the corresponding melting temperatures (1,200–1,300 °C). No phase transition was found for the H-type phase (R$\overline 3 $) with R=Sm–Tb and the L-type phase (P63 cm) with R=Tm–Yb. On the other hand, phase transition from the L phase to the H phase was observed for R=Dy–Er, and Y at around 1,100–1,200 °C. The obtained axial thermal expansion coefficient (ATEC) of the a-axis was larger than that of the c-axis for the H phase, and the ATEC of the c-axis was larger than that of the a-axis for the L phase. The observed anisotropic nature of ATEC is attributed to the distribution of the BO3 anionic group with rigid boron–oxygen bonding in the structures of the H and L phases.

Comparison of Silica Sand Properties from Kandal Province, Cambodia and Tapah, Perak, Malaysia and Characterization of Soda Lime Silicate Glass Produced From Cambodian Silica Sand

2013 ◽  
Vol 858 ◽  
pp. 248-253 ◽  
Author(s):  
Em Sereiratana ◽  
Khairul Anwar Bharum ◽  
S.A. Rezan ◽  
Radzali Othman ◽  
Fumitake Takahashi ◽  
...  
Keyword(s):  
Mechanical Properties ◽  
Particle Size ◽  
Melting Temperature ◽  
Size Range ◽  
Soda Lime ◽  
The Other ◽  
Silica Sand ◽  
Particle Size Range ◽  
Soaking Time ◽  
X Ray

Silica sand from Kandal province, Cambodia and Tapah Perak, Malaysia was grounded into an average micron size of 128.12 and 132.68µm. Both sands were characterized by X-ray fluorescence (XRF), X-ray Diffraction, particle Size Analysis, Differential Thermal Analysis and Thermogravimetric Analysis (DTA/TGA). Malaysian silica sand was designated SDMTP and Cambodian Silica sand as SDCK. From theanalysis, XRF showed that the major impurities in SDMTP were Al2O3, K2O and TiO2. On the other hand, SDCK had impurities of Al2O3,K2O and Na2O. DTA results from SDMTP and SDCK showedthere is an endothermic peak occurring at 572°C which can be attributed to β-quartz transformation into α-quartz. TGA for SDMTP showed that maximum weight lost was at 441°C with a weight percent (wt%) change of 0.48%. The TGA for SDCK showed a wt% change of 1.298% at temperature of 1000°C. From XRD analysis, the main phase of SDCK and SDMTP were quartz. The impurities of both sands play an important role in determining the optical and mechanical properties of the soda lime silicate (SLS) glass formed. Particle size of silica sand affects the mechanical properties such as compression, hardness, and transmittance of SLS glass. The smaller particle size would be ideal choice for glassmaking. Melting temperature, soaking time, and melt accelerant can also affect the mechanical properties of SLS glass. The best result obtained for Vickers hardness in this study was the SLS glass sample designated as Run No 12 with a value of 525.02 kg.mm-2. It had a particle size range from 500-600µm, a furnace soaking time of 4 hours at a melting temperature of 1500°C with 1.0 wt% of Sodium Chloride (NaCl) as meltingaccelerant. On the other hand, the highest compressive strength of 356.22 MPa was found in sample designated as Run No 1. It had a particle size range from 75-1800µm, a soaking time of 5 hours at a melting temperature of 1550°C with 0.5 wt% of NaCl. Lastly,the highest UV-VIS transmittance at 520 nm was obtained from sample designated as Run No 5 within the value of 84.26 %Transmittance (T). It had a particle size range of 75-1800µm, soaking time of 3 hours at a melting temperature of 1550°C with 1.5 wt% of NaCl. .

Electron microscopy of crystalline structure in thermotropic random copolymers

1991 ◽  
Vol 49 ◽  
pp. 1054-1055
Author(s):  
Afzana Anwer ◽  
S. Eilidh Bedford ◽  
Richard J. Spontak ◽  
Alan H. Windle
Keyword(s):  
Electron Microscopy ◽  
Crystalline Structure ◽  
Liquid Crystalline ◽  
Elevated Temperatures ◽  
Random Copolymers ◽  
Molecular Characteristics ◽  
Scanning Calorimetry ◽  
X Ray ◽  
Identical Monomer ◽  
Periodic Layer

Random copolyesters composed of wholly aromatic monomers such as p-oxybenzoate (B) and 2,6-oxynaphthoate (N) are known to exhibit liquid crystalline characteristics at elevated temperatures and over a broad composition range. Previous studies employing techniques such as X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) have conclusively proven that these thermotropic copolymers can possess a significant crystalline fraction, depending on molecular characteristics and processing history, despite the fact that the copolymer chains possess random intramolecular sequencing. Consequently, the nature of the crystalline structure that develops when these materials are processed in their mesophases and subsequently annealed has recently received considerable attention. A model that has been consistent with all experimental observations involves the Non-Periodic Layer (NPL) crystallite, which occurs when identical monomer sequences enter into register between adjacent chains. The objective of this work is to employ electron microscopy to identify and characterize these crystallites.

Microchemical imaging in biomedical research

1992 ◽  
Vol 50 (2) ◽  
pp. 1118-1119
Author(s):  
P. Ingram
Keyword(s):  
Data Analysis ◽  
Electron Probe ◽  
The Other ◽  
X Ray ◽  
Cell Element ◽  
Physiological Information ◽  
Functional States ◽  
Elemental Maps ◽  
Electron Energy Loss ◽  
Secondary Ion

It is well established that unique physiological information can be obtained by rapidly freezing cells in various functional states and analyzing the cell element content and distribution by electron probe x-ray microanalysis. (The other techniques of microanalysis that are amenable to imaging, such as electron energy loss spectroscopy, secondary ion mass spectroscopy, particle induced x-ray emission etc., are not addressed in this tutorial.) However, the usual processes of data acquisition are labor intensive and lengthy, requiring that x-ray counts be collected from individually selected regions of each cell in question and that data analysis be performed subsequent to data collection. A judicious combination of quantitative elemental maps and static raster probes adds not only an additional overall perception of what is occurring during a particular biological manipulation or event, but substantially increases data productivity. Recent advances in microcomputer instrumentation and software have made readily feasible the acquisition and processing of digital quantitative x-ray maps of one to several cells.

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