THE FORMATION AND PROPERTIES OF THREE-DIMENSIONAL POLYMERS: III. THE EFFECT OF NETWORK STRUCTURE ON ELASTIC PROPERTIES

1949 ◽  
Vol 27b (2) ◽  
pp. 139-150 ◽  
Author(s):  
J. Bardwell ◽  
C. A. Winkler
Keyword(s):  
Molecular Weight ◽  
Statistical Mechanics ◽  
Elastic Properties ◽  
Network Structure ◽  
Three Dimensional ◽  
Butyl Rubber ◽  
Rubber Elasticity ◽  
Cross Linking

The tension exerted by stretched rubber at a given temperature and elongation is determined by the initial molecular weight and the concentration of cross-linkages. With the copolymer of butadiene and styrene (GR-S) the effect of molecular weight on elastic properties is identical with that found by Flory for butyl rubber and arises from the inactivity of terminal chains. When the molecular weight is fixed, the retractive force is approximately linear with the degree of cross-linking, in agreement with the statistical mechanics of rubber elasticity.

Dependence of Elastic Properties of Vulcanized Rubber on the Degree of Cross-Linking

1950 ◽  
Vol 23 (1) ◽  
pp. 9-26
Author(s):  
Paul J. Flory ◽  
Norman Rabjohn ◽  
Marcia C. Shaffer
Keyword(s):  
Statistical Theory ◽  
Network Structure ◽  
Short Circuit ◽  
Elastic Equilibrium ◽  
Butyl Rubber ◽  
Rubber Elasticity ◽  
Cross Linking ◽  
Substantial Part ◽  
Vulcanized Rubber ◽  
Low Degrees

Abstract The results reported above demonstrate a progressive increase in the force of retraction τ at fixed elongation with increase in the fraction p of the structural units which are cross-linked from ρ=0.10×10−2 to 3.0×10−2. Over this range, τ at 100 per cent elongation increases about thirteenfold. Swelling measurements indicate that the increase in τ with ρ continues over an additional tenfold range in ρ. Previous assertions that the modulus of elasticity of soft gum rubber vulcanizates depends largely on chain interaction and entanglements other than those imposed by the cross-linkages, and that the modulus is, therefore, not directly related to the degree of cross-linking, are without foundation. The statistical theory of rubber elasticity expresses the force of retraction as a function of the temperature, vulcanizate structure and elongation; no arbitrary constants are involved. The magnitudes of τ for α=2 are in remarkably close agreement with the predictions of the theory over most of the range in ρ. This fact is of the utmost significance in confirmation of the statistical theory of rubber elasticity and of the analysis of the network structure of vulcanized rubber. On the other hand, τ increases less rapidly with ρ than the direct proportionality prescribed by theory. Forces of retraction are higher than the theory predicts at low degrees of cross-linking, and an opposite deviation is observed for values of ρ greater than about 1×10−2. Previous observations on Butyl rubber, vulcanized to p values from about 0.16×10−2 to 0.28×10−2 indicated forces of retraction (for infinite molecular weight M) which exceed by about threefold those predicted from the theory. This deviation is decidedly larger than has been observed here in the same range for ρ. A substantial part of the discrepancy observed for Butyl rubber may have arisen from failure to secure elastic equilibrium, however. Deviations in the values of τ from theory probably originate largely from oversimplifications in the treatment of the network structure. Entanglements of the sort previously discussed tend to enhance the restraints imposed on the chains when the rubber is elongated. Their percentage effect should be greatest for low degrees of cross-linking, hence the observed τ values are higher than theory at low degrees of cross-linking. “Intramolecular” cross-linkages, yielding short-circuit structures contributing nothing to the elastic reaction of the network, should become increasingly important at higher degrees of cross linking. Such wastage of cross-linkages may account for the low values of τ obtained for higher ρ values.

THE FORMATION AND PROPERTIES OF THREE-DIMENSIONAL POLYMERS: I. STATISTICS OF NETWORK POLYMERS

1949 ◽  
Vol 27b (2) ◽  
pp. 116-127 ◽  
Author(s):  
J. Bardwell ◽  
C. A. Winkler
Keyword(s):  
Molecular Weight ◽  
Chain Transfer ◽  
Three Dimensional ◽  
Insoluble Fraction ◽  
Cross Linking ◽  
Molecular Heterogeneity ◽  
Swelling Properties ◽  
Network Polymers ◽  
Probable Distribution ◽  
Most Probable Distribution

Theoretical treatments of the elastic and swelling properties of three-dimensional polymers are reviewed and the predicted influence of network structure discussed. An expression is obtained for the statistically most probable distribution of molecular weight for polymers terminated by chain transfer with a modifier. Depletion of modifier does not lead to a large increase in molecular heterogeneity. The formation of an insoluble fraction and the development of cyclic structures when such polymers are subjected to cross-linking conditions are treated by an application of the theory of gelation.

The Formation and Structure of Vulcanizates

1949 ◽  
Vol 22 (1) ◽  
pp. 96-104
Author(s):  
J. Bardwell ◽  
C. A. Winkler
Keyword(s):  
Mechanical Properties ◽  
Molecular Weight ◽  
Physical Properties ◽  
Network Structure ◽  
Weight Distribution ◽  
Elastic Behavior ◽  
Cross Linking ◽  
Structural Factors ◽  
Experimental Proof ◽  
Vulcanized Rubber

Abstract The characteristic mechanical properties of vulcanized rubber are believed to result from a network structure made up of chainlike molecules bonded together by occasional cross-linkages. In relating the physical properties of the vulcanizate to the structure of the network, it is therefore necessary to consider the concentration of cross-linkages and the molecular-weight distribution of the rubber molecules before cross-linking. Various theories have been proposed for the dependence of elastic properties on these structural factors, but experimental proof of the suggested relations has been meager, largely because of the complexities met with in, vulcanization reactions. In the present investigation some of these difficulties have been overcome, and the quantitative relations between the elastic behavior of GR-S and its network structure have thereby been revealed.

Electron Microscopy and image reconstruction reveal the structural basis for spectrin's elastic properties

1992 ◽  
Vol 50 (1) ◽  
pp. 510-511
Author(s):  
Amy M. McGough ◽  
Robert Josephs
Keyword(s):  
Electron Microscopy ◽  
Elastic Properties ◽  
Conformational Changes ◽  
Quaternary Structure ◽  
Three Dimensional ◽  
Membrane Skeleton ◽  
Projection Algorithm ◽  
Structural Basis ◽  
Iterative Approximation ◽  
Membrane Skeletons

The remarkable deformability of the erythrocyte derives in large part from the elastic properties of spectrin, the major component of the membrane skeleton. It is generally accepted that spectrin's elasticity arises from marked conformational changes which include variations in its overall length (1). In this work the structure of spectrin in partially expanded membrane skeletons was studied by electron microscopy to determine the molecular basis for spectrin's elastic properties. Spectrin molecules were analysed with respect to three features: length, conformation, and quaternary structure. The results of these studies lead to a model of how spectrin mediates the elastic deformation of the erythrocyte.Membrane skeletons were isolated from erythrocyte membrane ghosts, negatively stained, and examined by transmission electron microscopy (2). Particle lengths and end-to-end distances were measured from enlarged prints using the computer program MACMEASURE. Spectrin conformation (straightness) was assessed by calculating the particles’ correlation length by iterative approximation (3). Digitised spectrin images were correlation averaged or Fourier filtered to improve their signal-to-noise ratios. Three-dimensional reconstructions were performed using a suite of programs which were based on the filtered back-projection algorithm and executed on a cluster of Microvax 3200 workstations (4).

Cross-Linked αsγt-Chain Hybrids in Plasma Clots Studied by 1D- and 2D Electrophoresis and Western Blotting

1993 ◽  
Vol 70 (03) ◽  
pp. 438-442 ◽  
Author(s):  
B Grøn ◽  
C Filion-Myklebust ◽  
S Bjørnsen ◽  
P Haidaris ◽  
F Brosstad
Keyword(s):  
Molecular Weight ◽  
Monoclonal Antibodies ◽  
Human Plasma ◽  
Western Blotting ◽  
Isoelectric Point ◽  
Factor Xiii ◽  
Cross Linking ◽  
2D Electrophoresis ◽  
Complex Phenomenon ◽  
Fibrinopeptide A

SummaryFibrinogen and fibrin related chains in reduced human plasma as well as the bonds interlinking partially cross-linked fibrin from plasma clots have been studied by means of 1D- and 2D electrophoresis and Western blotting. Immunovisualization of reduced plasma or partially cross-linked fibrin with monoclonal antibodies specific for the α-chains or the γ-chains have shown that several bands represent material belonging to both chains. In order to decide whether these bands constitute αγ-chain hybrids or superimposed α- and γ-chain dimers, the cross-linked material was separated according to both isoelectric point (pI) and molecular weight (MW) using Pharmacia’s Multiphor II system. Western blotting of the second dimension gels revealed that partially cross-linked fibrin contains αsγt-chain hybrids and γ- polymers, in addition to the well-known γ-dimers and α-polymers. The main αsγt-chain hybrid has a pI between that of the α- and the γ-chains, a MW of about 200 kDa and contains Aα-chains with intact fibrinopeptide A (FPA). It was also observed that soluble fibrinogen/fibrin complexes as well as partially cross-linked fibrin contain degraded α-dimers with MWs close to the γ-dimers. These findings demonstrate that factor XIII-catalyzed cross-linking of fibrin is a more complex phenomenon than earlier recognized.

scholarly journals Mechanical Behavior of Hydroxyapatite-Chitosan Composite: Effect of Processing Parameters

Minerals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 213
Author(s):  
Hamid Ait Said ◽  
Hassan Noukrati ◽  
Hicham Ben Youcef ◽  
Ayoub Bayoussef ◽  
Hassane Oudadesse ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Compressive Strength ◽  
Mechanical Strength ◽  
Bone Repair ◽  
Mechanical Stability ◽  
Three Dimensional ◽  
Processing Parameters ◽  
Composite Effect ◽  
Solid Liquid ◽  
The Impact

Three-dimensional hydroxyapatite-chitosan (HA-CS) composites were formulated via solid-liquid technic and freeze-drying. The prepared composites had an apatitic nature, which was demonstrated by X-ray diffraction and Infrared spectroscopy analyses. The impact of the solid/liquid (S/L) ratio and the content and the molecular weight of the polymer on the composite mechanical strength was investigated. An increase in the S/L ratio from 0.5 to 1 resulted in an increase in the compressive strength for HA-CSL (CS low molecular weight: CSL) from 0.08 ± 0.02 to 1.95 ± 0.39 MPa and from 0.3 ± 0.06 to 2.40 ± 0.51 MPa for the HA-CSM (CS medium molecular weight: CSM). Moreover, the increase in the amount (1 to 5 wt%) and the molecular weight of the polymer increased the mechanical strength of the composite. The highest compressive strength value (up to 2.40 ± 0.51 MPa) was obtained for HA-CSM (5 wt% of CS) formulated at an S/L of 1. The dissolution tests of the HA-CS composites confirmed their cohesion and mechanical stability in an aqueous solution. Both polymer and apatite are assumed to work together, giving the synergism needed to make effective cylindrical composites, and could serve as a promising candidate for bone repair in the orthopedic field.

scholarly journals Enhanced bacterial disinfection by CuI–BiOI/rGO hydrogel under visible light irradiation

RSC Advances ◽  
2021 ◽  
Vol 11 (33) ◽  
pp. 20446-20456
Author(s):  
Xi Ma ◽  
Ziwei Wang ◽  
Haoguo Yang ◽  
Yiqiu Zhang ◽  
Zizhong Zhang ◽  
...  
Keyword(s):  
Electron Transport ◽  
Visible Light ◽  
Network Structure ◽  
Visible Light Irradiation ◽  
Three Dimensional ◽  
Light Irradiation ◽  
Transport Capacity ◽  
Highly Efficient ◽  
Dimensional Network ◽  
Bacterial Disinfection

Compared with traditional layered graphene, graphene hydrogels have been used to construct highly efficient visible light-excited photocatalysts due to their particular three-dimensional network structure and efficient electron transport capacity.

scholarly journals Effect of Oat β-Glucan on the Rheological Characteristics and Microstructure of Set-Type Yogurt

Molecules ◽  
2021 ◽  
Vol 26 (16) ◽  
pp. 4752
Author(s):  
Xiaoqing Qu ◽  
Yuliya Nazarenko ◽  
Wei Yang ◽  
Yuanyang Nie ◽  
Yongsheng Zhang ◽  
...  
Keyword(s):  
Sensory Evaluation ◽  
Network Structure ◽  
Theoretical Basis ◽  
Fermentation Process ◽  
Three Dimensional ◽  
Rheological Characteristics ◽  
Fermentation Time ◽  
Spherical Aggregate ◽  
Dimensional Network ◽  
Solid Liquid

The oat β-glucan (OG) was added into set-type yogurt as a functional ingredient, in order to evaluate effects on the rheological characteristics and microstructure of set-type yogurt. When the OG concentration increased from 0 to 0.3%, the WHC gradually increased. At 0.3% OG, the set-type yogurt had the highest WHC of 94.67%. Additionally, the WHC continuously decreased, reaching the lowest WHC (about 80%) at 0.5% OG. When 0.3% OG was added, the highest score of sensory evaluation was about 85. The rheological result showed that the fermentation process went through the changes as follows: solid → liquid → solid → liquid. The addition of 0.3% OG decreased the fermentation time of set-type yogurt by about 16 min, making yogurt more inclined to be liquid. The acidity of set-type yogurt with OG was slightly higher. The result of microstructure showed that the addition of OG destroyed the three-dimensional network structure of yogurt, and some spherical aggregate particles could be clearly observed at 0.3% OG. Overall, this study provided a theoretical basis for the application of OG in set-type yogurt.

scholarly journals Characterization of Polycaprolactone Nanohydroxyapatite Composites with Tunable Degradability Suitable for Indirect Printing

Polymers ◽  
2021 ◽  
Vol 13 (2) ◽  
pp. 295
Author(s):  
Stephanie E. Doyle ◽  
Lauren Henry ◽  
Ellen McGennisken ◽  
Carmine Onofrillo ◽  
Claudia Di Bella ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Large Scale ◽  
Three Dimensional ◽  
Cell Number ◽  
Compressive Modulus ◽  
Degradation Rates ◽  
Scaffold Materials ◽  
Natural Tissue ◽  
Complete Regeneration

Degradable bone implants are designed to foster the complete regeneration of natural tissue after large-scale loss trauma. Polycaprolactone (PCL) and hydroxyapatite (HA) composites are promising scaffold materials with superior mechanical and osteoinductive properties compared to the single materials. However, producing three-dimensional (3D) structures with high HA content as well as tuneable degradability remains a challenge. To address this issue and create homogeneously distributed PCL-nanoHA (nHA) scaffolds with tuneable degradation rates through both PCL molecular weight and nHA concentration, we conducted a detailed characterisation and comparison of a range of PCL-nHA composites across three molecular weight PCLs (14, 45, and 80 kDa) and with nHA content up to 30% w/w. In general, the addition of nHA results in an increase of viscosity for the PCL-nHA composites but has little effect on their compressive modulus. Importantly, we observe that the addition of nHA increases the rate of degradation compared to PCL alone. We show that the 45 and 80 kDa PCL-nHA groups can be fabricated via indirect 3D printing and have homogenously distributed nHA even after fabrication. Finally, the cytocompatibility of the composite materials is evaluated for the 45 and 80 kDa groups, with the results showing no significant change in cell number compared to the control. In conclusion, our analyses unveil several features that are crucial for processing the composite material into a tissue engineered implant.

Sign in / Sign up

Export Citation Format

Share Document