Effect of Strain on Thermodynamic Melting Temperature of Polymers

1967 ◽  
Vol 40 (3) ◽  
pp. 788-800
Author(s):  
W. R. Krigbaum ◽  
J. V. Dawkins ◽  
G. H. Via ◽  
Y. I. Balta
Keyword(s):  
Free Energy ◽  
Melting Point ◽  
Natural Rubber ◽  
Sonic Velocity ◽  
X Ray Diffraction ◽  
Elongation Ratio ◽  
Flory Theory ◽  
X Ray ◽  
Theoretical Predictions ◽  
Crystallization Conditions

Abstract X-ray diffraction, sonic velocity, and birefringence measurements were used to study the variation of the apparent melting point of strained natural rubber and polychloroprene vulcanizates with elongation ratio and crystallization temperature. The procedure of Hoffman and Weeks was employed to obtain the thermodynamic melting point, tm, for each elongation ratio α. The parameter β relating to the distribution of fold lengths is unusually large for low elongation ratios and decreases into the usual range only at higher elongations. Observed variations of tm with α for these two polymers are compared with the theoretical predictions of Flory and Roe and Krigbaum. Although the predictions of the Flory theory depend somewhat upon the value assigned for the number of repeating units per statistical link, and this parameter is not well known for polychloroprene, we nevertheless conclude that his treatment offers a better representation of the melting point elevation for high elongations. Due to the approximations introduced, the treatment of Flory is not valid for lower elongations. Any attempt to improve this treatment must begin by specifying the free energy of the semicrystalline system, which implies a knowledge of the distribution of crystallite orientations and how this distribution varies with strain and with the crystallization conditions.

Polydomain Structure of Epitaxial PbTiO3 films on MgO

1997 ◽  
Vol 493 ◽  
Author(s):  
S. P. Alpay ◽  
A. S. Prakash ◽  
S. Aggarwal ◽  
R. Ramesh ◽  
A. L. Roytburd ◽  
...  
Keyword(s):  
Domain Structure ◽  
Pulsed Laser ◽  
Laser Deposition ◽  
X Ray Diffraction ◽  
X Ray ◽  
Theoretical Predictions ◽  
The Stability ◽  
Increasing Temperature ◽  
Stable Domains ◽  
Domain Stability

ABSTRACTA PbTiO3(001) film grown on MgO(001) by pulsed laser deposition is examined as an example to demonstrate the applications of the domain stability map for epitaxial perovskite films which shows regions of stable domains and fractions of domains in a polydomain structure. X-ray diffraction studies indicate that the film has a …c/a/c/a… domain structure in a temperature range of °C to 400°C with the fraction of c-domains decreasing with increasing temperature. These experimental results are in excellent agreement with theoretical predictions based on the stability map.

Structural and thermodynamic properties of nanocrystalline fcc metals prepared by mechanical attrition

1992 ◽  
Vol 7 (7) ◽  
pp. 1751-1761 ◽  
Author(s):  
J. Eckert ◽  
J.C. Holzer ◽  
C.E. Krill ◽  
W.L. Johnson
Keyword(s):  
Thermal Analysis ◽  
Grain Size ◽  
Melting Point ◽  
Grain Boundary ◽  
Bulk Modulus ◽  
Atomic Level ◽  
X Ray Diffraction ◽  
X Ray ◽  
Fcc Metals ◽  
Mechanical Attrition

Nanocrystalline fcc metals have been synthesized by mechanical attrition. The crystal refinement and the development of the microstructure have been investigated in detail by x-ray diffraction, differential scanning calorimetry, and transmission electron microscopy. The deformation process causes a decrease of the grain size of the fcc metals to 6–22 nm for the different elements. The final grain size scales with the melting point and the bulk modulus of the respective metal: the higher the melting point and the bulk modulus, the smaller the final grain size of the powder. Thus, the ultimate grain size achievable by this technique is determined by the competition between the heavy mechanical deformation introduced during milling and the recovery behavior of the metal. X-ray diffraction and thermal analysis of the nanocrystalline powders reveal that the crystal size refinement is accompanied by an increase in atomic-level strain and in the mechanically stored enthalpy in comparison to the undeformed state. The excess stored enthalpies of 10–40% of the heat of fusion exceed by far the values known for conventional deformation processes. The contributions of the atomic-level strain and the excess enthalpy of the grain boundaries to the stored enthalpies are critically assessed. The kinetics of grain growth in the nanocrystalline fcc metals are investigated by thermal analysis. The activation energy for grain boundary migration is derived from a modified Kissinger analysis, and estimates of the grain boundary enthalpy are given.

Dolomite Decomposition to (Ca,Mg)O Solid Solutions: An X-Ray Diffraction Study.Part II.

1984 ◽  
Vol 39 (10) ◽  
pp. 981-985 ◽  
Author(s):  
G. Spinolo ◽  
U. Anselmi Tamburini
Keyword(s):  
Free Energy ◽  
Low Temperatures ◽  
Particle Sizes ◽  
Diffusional Process ◽  
X Ray Diffraction ◽  
High Iron Content ◽  
X Ray ◽  
Energy Of Mixing ◽  
Free Energy Of Mixing ◽  
Low Pressures

Abstract The full decomposition of dolomites with low and high iron content at low temperatures and low pressures is discussed with reference to the free energy of mixing of the ternary system Ca. Fe, Mg/O. The actual products of the primary step are a couple of rock salt structured oxides close to the spinodal compositions and with very small particle sizes. A subsequent diffusional process can produce large crystallites with equilibrium compositions, but it is effective only when either a low-iron dolomite is used as starting material or higher temperatures are employed.

scholarly journals Superionic Solid Electrolyte Li7La3Zr2O12 Synthesis and Thermodynamics for Application in All-Solid-State Lithium-Ion Batteries

Materials ◽  
2021 ◽  
Vol 15 (1) ◽  
pp. 281
Author(s):  
Daniil Aleksandrov ◽  
Pavel Novikov ◽  
Anatoliy Popovich ◽  
Qingsheng Wang
Keyword(s):  
Free Energy ◽  
Solid State ◽  
Lithium Ion Batteries ◽  
Gibbs Free Energy ◽  
Thermodynamic Characteristics ◽  
Lithium Ion ◽  
Standard Enthalpy Of Formation ◽  
X Ray Diffraction ◽  
X Ray ◽  
Binary Compounds

Solid-state reaction was used for Li7La3Zr2O12 material synthesis from Li2CO3, La2O3 and ZrO2 powders. Phase investigation of Li7La3Zr2O12 was carried out by x-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDS) methods. The thermodynamic characteristics were investigated by calorimetry measurements. The molar heat capacity (Cp,m), the standard enthalpy of formation from binary compounds (ΔoxHLLZO) and from elements (ΔfHLLZO), entropy (S0298), the Gibbs free energy of the Li7La3Zr2O12 formation (∆f G0298) and the Gibbs free energy of the LLZO reaction with metallic Li (∆rGLLZO/Li) were determined. The corresponding values are Cp,m = 518.135 + 0.599 × T − 8.339 × T−2, (temperature range is 298–800 K), ΔoxHLLZO = −186.4 kJ·mol−1, ΔfHLLZO = −9327.65 ± 7.9 kJ·mol−1, S0298 = 362.3 J·mol−1·K−1, ∆f G0298 = −9435.6 kJ·mol−1, and ∆rGLLZO/Li = 8.2 kJ·mol−1, respectively. Thermodynamic performance shows the possibility of Li7La3Zr2O12 usage in lithium-ion batteries.

Optimization of Structure of Soft Block for Design of Adaptive Polyurethanes

2020 ◽  
Vol 869 ◽  
pp. 273-279
Author(s):  
Marina A. Gorbunova ◽  
Denis V. Anokhin ◽  
Valentina A. Lesnichaya ◽  
Alexander A. Grishchuk ◽  
Elmira R. Badamshina
Keyword(s):  
Mutual Influence ◽  
Glycol Adipate ◽  
Mass Ratio ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
X Ray ◽  
Crystallization Conditions ◽  
Crystalline Domains ◽  
Kinetics Of

A synthesis of new di-and triblock polyurethane thermoplastic copolymers containing different mass ratio of two crystallizing blocks - poly (1,4-butylene glycol) adipate and poly-ε-caprolactone diols was developed. Using combination of danamometric analysis, IR-spectroscopy, differential scanning calorimetry and X-ray diffraction, the effect of the soft block composition and crystallization conditions on crystal structure and thermal behavior of the obtained polymers have been studied. For the triblock copolymers we have shown a possibility of control the kinetics of material hardening and final mechanical characteristics due to the mutual influence of polydiols during crystallization. In the result, the second crystallizing component allows to control amount, structure and quality of crystalline domains in polyurethanes by variation of crystallization conditions.

Crystal Structure and Colorimetric Behavior of Low Melting Point Ternary Alloy

2020 ◽  
Vol 1002 ◽  
pp. 12-20
Author(s):  
Tarik T. Issa ◽  
Sadeer M. Majeed ◽  
Duha S. Ahmed
Keyword(s):  
Crystal Structure ◽  
Melting Point ◽  
Mechanical Alloying ◽  
Ternary Alloy ◽  
High Purity ◽  
Milling Time ◽  
X Ray Diffraction ◽  
X Ray ◽  
Before And After

Elements of high purity (99.999) ,were used to prepare the alloy , Bi ,Sn,Zn and Cu .Two types alloy Bi – Sn – Zn and Bi – Sn – Cu were prepared by mechanical alloying technique (MA) .Annealing at 100 °Cfor 8 hours was applied for the resulting alloys . X-ray diffraction and differential scanning colorimetriy were tested for the two types of alloy before and after annealing. The best results was noticed in the ternary alloythat prepared at 4 hours milling time ,and annelid at 100 °C, for 8 hours ,under static air.

Strong Deviation Of The Lattice Parameter In Si1-x-yGexCy Epilayers From Vegard's Rule

1998 ◽  
Vol 533 ◽  
Author(s):  
J. Stangl ◽  
S. Zerlauth ◽  
F. Schäffler ◽  
G. Bauer ◽  
M. Berti ◽  
...  
Keyword(s):  
Lattice Spacing ◽  
Lattice Parameter ◽  
Negative Deviation ◽  
X Ray Diffraction ◽  
X Ray ◽  
Strong Deviation ◽  
Theoretical Predictions

AbstractFrom the comparison of precise determinations of the Ge and C contents of a series of Si1-x-yGexCy epilayer samples (x < 0.18, y < 0.02) by Rutherford and resonant backscattering experiments and x-ray diffraction, the variation of the Si1-x-yGexCy lattice spacing as a function of C content is determined. A significant negative deviation from Vegard's rule is observed, in agreement with theoretical predictions by Kelires.

scholarly journals The Orientation of Strain-Induced Crystallites in Uniaxially-Strained, Thin and Wide Bands Made from Natural Rubber

Crystals ◽  
2019 ◽  
Vol 9 (6) ◽  
pp. 294 ◽  
Author(s):  
Konrad Schneider ◽  
Matthias Schwartzkopf
Keyword(s):  
Natural Rubber ◽  
Pure Shear ◽  
Orientation Distribution ◽  
Thin Strip ◽  
X Ray Diffraction ◽  
Reinforcing Effect ◽  
X Ray ◽  
Crack Tips ◽  
Strain Induced Crystallization ◽  
Induced Crystallization

Vulcanized natural rubber (unfilled and filled with 20 phr carbon black) is strained. We suppress the macroscopic formation of fiber symmetry by choosing strip-shaped samples ("pure-shear geometry") and investigate the orientation of the resulting crystallites by two-dimensional wide-angle X-ray diffraction (WAXD), additionally rotating the sample tape about the straining direction. Indications of a directed reinforcing effect of the strain-induced crystallization (SIC) in the thin strip are found. In the filled material fewer crystallites are oriented and the orientation distribution of the oriented crystallites is less perfect. The results confirm, that it is important for the evaluation of crystallinity under deformation to check, whether fiber symmetry can be assumed. This has consequences in particular on the quantitative interpretation of space-resolved scanning experiments in the vicinity of crack tips. Furthermore it raises the question, whether there is an asymmetric reinforcing effect of the SIC in the vicinity of crack tips inside natural rubber.

New Aspects on Melting and Annealing Behaviour of Polymers

1978 ◽  
Vol 33 (12) ◽  
pp. 1472-1483
Author(s):  
J. Haase ◽  
S. Köhler ◽  
R. Hosemann
Keyword(s):  
Free Energy ◽  
Melting Point ◽  
Partial Melting ◽  
Surface Free Energy ◽  
Average Crystallite Size ◽  
X Ray ◽  
State Diffusion ◽  
Crystallite Sizes ◽  
Dta Curves ◽  
Dta Curve

Abstract Poly( 1-butene) (PB) crystallizes from the melt in a metastable modification II (mod. II) which slowly transforms into the stable modification I (mod. I). X-ray wide angle (WAXS) measurements show that in mod. I the size of the microparacrystallites (mPC’s) in chain direction, D̅012, the polydispersity gD of the size distribution in this direction, the lateral size D̅110 and the paracrystalline g110-value do not change upon annealing at temperatures up to the melting point. In mod. II, however, the sizes D̅012 and D̅110 increase with rising annealing temperature Tann. At a certain Tann and beyond a sufficient annealing time tann the size D̅012 shows a logarithmic increase with tann whereas D̅110 stays constant. Measuring melting points Tm of mod. I-samples, we found a linear relationship between Tm and 1/D̅012 according to the Thomson equation resulting in a melting point for an infinite crystal of Tm∞ (mod. I) = 139 °C and a mean surface free energy of σ̅e′̅ (mod. I) = 47 ergs/cm2. T m versus 1/D̅012 for mod. II is linear only for high D̅012-values yielding Tm∞ (mod. II) = 130 °C and σ̅e′̅ (mod. II) = 29 ergs/cm2. However, a partially molten and afterwards quenched sample of mod. I with small mPC’s shows a mod. II-peak which fits the straight line extrapolated from the large D̅012-values. The DTA curves of mod. I-samples shift to higher temperatures and narrow after annealing although the crystallite sizes and size distributions remain as well as the paracrystalline distortions the same. X-ray and DTA measurements eliminate therefore surface premelting and selective melting of thinner and more distorted lamellae in mod. I. Upon annealing this modification, σ̅e′̅ decreases from 47 ergs/cm2 to 15 ergs/cm2 and the distribution of σe′ narrows. The latter determines predominantly the shape of the DTA curve. The Thomson equation therefore, applied to different samples links only the average crystallite size and the mean surface free energy with the melting point. In mod. I partial melting occurs independent of D̅012 and starts mainly at those mPC’s which have exposed surfaces with high σe′. At the beginning only single mPC’s or single lamellae melt, but no bundles of lamellae. The logarithmic increase of D̅012 in mod. II with tann can be explained according to Hosemann’s model of “lateral melting” also by a partial melting of mPC’s with unprotected lateral surfaces and by a consecutive solid state diffusion of their chainsegments into the two mPC’s adjacent in chain direction, increasing the averaged sizes of the long period and the lamellae thickness.

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