Kinetic behavior of UV-sensitive polymers from modified natural rubber

Photosensitive copolymers have been obtained by chemical modification of natural rubber. The introduction of the photoreactive cinnamoyl group in different conversions has been carried out by the reaction of natural polyisoprene with maleic anhydride, followed by ring opening and condensation with some oxyalkylcinnamate esters. These reactions gave rise to five polymer series. Each series, for which the anhydride content was kept constant, is constituted of five copolymeric products, differing from each other in the size of the aliphatic chain between the chromophore and the main chain. The photosensitive products were submitted to UV irradiation, and their kinetic behavior has been investigated in order to correlate structural dissimilarities with the dimerization rate constants.     

The effect of natural rubber crosslink density on real time birefringence,true stress and true strain behavior

A newly developed real time spectral birefringence technique was implemented to follow the coupled relationships between birefringence, true stress and true strain behavior of varying crosslink density natural rubber vulcanizates at room temperature. It was shown that the stress optical law is valid even at early stages of crystallization during stretching and there exists a critical birefringence beyond which the metastable “near perfect” oriented and highly distorted crystalline regions form and upon retraction this crystalline order disappears at the same critical birefringence level. These crystalline regions exhibit nematic order with significant axial registry distortions at early stages of the formation. They are suggested to form at or near the juncture points of the chemical network formed by crosslinks, and physical network by chain entanglements where the orientability of the chains is the most efficient.     

Effects of gamma-radiation on natural rubber vulcanizates under tension

The effect of γ-radiation on natural rubber vulcanizates under mechanical strain has been investigated with reference to the effect of antidegradants, fillers and vulanization system. Samples were irradiated in the dose range of 5–15 Mrad in air at room temperature (25°C) at a rate of 0.3 Mrad/h. Sol content and volume fraction of vulcanizates were also determined to gain insight into the network structure of the irradiated vulcanizates. Natural rubber vulcanizates undergo molecular scission which in effect cause a decrease in tensile strength. Generally the 300% modulus increases, the increment being more prominent at lower radiation dose. The fall in tensile strength is also high at higher doses of radiation. Carbon black and antidegradants protect rubber from γ-radiation.     

Effect of crosslink density on the creep behavior of natural rubber vulcanizates

Torsional creep measurements on four natural rubber vulcanizates, crosslinked to different degrees, were carried out in the temperature range from ?50 to 90°C. This investigation complements the studies on identical samples of the stress relaxation behavior by Chasset and Thirion and of the dynamic mechanical response by Ferry, Mancke, Maekawa, ōyanagi, and Dickie. The creep measurements reported are shown to be in agreement with the stress relaxation results. In addition to the usual temperature reduction, a superposed curve was obtained for the long time response using the apparent molecular weight between crosslinks, M_c, as a reduction variable. The variation in viscoelastic response with crosslink density is interpreted as a restrictive action of the chemical crosslinks on the transient entanglement network.     

Protein-free natural rubber

Some properties of protein-free natural rubber were investigated by measurements of both water uptake and stress versus strain. The protein-free natural rubber was prepared in latex stage by the novel procedure to remove all proteins from natural rubber with urea and a polar organic solvent in the presence of surfactant, which had been developed in our recent work. First, the condition for the removal of the proteins was investigated in terms of affinity of the polar organic solvents, concentration of the solvents, type of surfactant, and repeating times for washing latex with a centrifuge. Acetone and anionic surfactant were found to be effective for the removal of the proteins. Under an optimum condition, total nitrogen content and amount of extractable proteins of deproteinized natural rubber were 0.000 w/w% and 0.00 μg/ml, respectively. The removal of the proteins from natural rubber was confirmed through Fourier transform infrared (FT-IR) spectroscopy. Water uptake, hydration, and tensile strength of the rubbers were measured by water swelling method, FT-IR spectroscopy, and measurement of stress versus strain, respectively. The water uptake and the hydration were dependent upon the content of the proteins. The tensile strength of the rubbers, which were prepared to be as-cast films without crosslinking, decreased after removal of the all proteins.     

Interplay of rubber network theory with the damping behavior of crosslinked polyurethanes

Network formation (branching) theory was used to examine the relationships between network structure and concomitant sound and vibration damping. For a series of model polyether-based polyurethane networks with varying stoichiometry and composition, the glass transition temperature T_g, was found to increase with increasing concentration of elastically active network chains, EANCs, as well as the ratio of branch OH group concentration to the total OH group concentration ρ. The values of (tan δ)_max, the peak height of tan δ at T_g, linearly decrease with increasing concentration of EANCs, regardless of the ρ values. However, the loss area (LA), equal to the integral of the linear loss modulus-temperature curve, is independent of the concentration of EANCs and/or ρ. Utilizing group contribution analysis techniques, the value of the main chain -O- group contribution, LA_-O-, is 19.1 GPa·K/g, a rather large value. This finding gives insight into why polyether urethanes are preferred for many damping applications.     

Biomolecules under mechanical stress: a simple mechanism of complex behavior

The unfolding of a biomolecule by stretching force is commonly treated theoretically as one-dimensional dynamics along the reaction coordinate coincident with the direction of pulling. Here we explore a situation, particularly relevant to complex biomolecules, when the pulling direction alone is not an adequate reaction coordinate for the unfolding or rupture process. We show that in this case the system can respond to pulling force in unusual ways. Our theory points out a remarkably simple, but largely overlooked, mechanism of the complex responses of biomolecules to force. The mechanism originates from the basic property of the transition state to change its structure under applied force. A relationship is established between a key experimental observable--force-dependent lifetime--and the microscopic properties of the biomolecule in the form of an analytical solution to the problem of a force-induced molecular transition in two dimensions. The theory is applicable to biological contexts ranging from protein folding to ligand-receptor interactions.     

Thermal behavior of chitosan/natural rubber latex blends TG and DSC analysis

The thermal behavior of chitosan (CS)/natural rubber latex (NRL) blends has been studied by thermogravimetry (TG) and differential scanning calorimetry (DSC). Decomposition behavior of CS changes with the addition of NRL. The effect of blend composition on the amount of residue remaining at various temperatures has been studied. Activation energies of degradation have been calculated using Horowitz-Metzger equation. From the activation energy values, it is found that among the series of the blend compositions, CS₁₅NRL₈₅ exhibits better thermal stability. DSC studies reveals that the CS/NRL blends are thermodynamically incompatible. This is evident from the presence of two glass transitions, corresponding to CS and NRL phases in the blend.     

Analysis of the thermogenesis mechanism of natural rubber under high speed strain

This work highlights the relationship of crosslink density, entanglement points and various sulfide crosslinks with the thermogenesis properties of natural rubber (NR). The impact of cross‐link and entanglement on thermogenesis properties was evaluated by heat build‐up test, swelling behavior, statistical thermodynamic calculation, and classic viscoelastic theory. It was found that cross‐link and entanglement points have “pinning” effect to the rubber chain, thus remarkably restricting the motion of the rubber chain and reducing thermogenesis. Besides, the effects of various sulfide crosslinks and cross‐link length on thermogenesis were compared and discussed varying the sulfur vulcanization system. It was found that the semi‐effective vulcanization system using N‐cyclohexyl‐2‐benzothiazolesulfenamide (CZ) and 2‐Mercaptobenzothiazole (M) has the lowest thermogenesis (bottom temperature rise is 7.5°C, middle is 18.7°C), which on account of combined short crosslink length with high rigid rubber chain (crosslink network dominated by mono‐ and disulfides). As a result, the deformation degree of the rubber chain during curl up‐extension and the thermogenesis are further reduced. Finally, a combination of natural film coagulation and semi‐effective vulcanization system was used to prepare a low thermogenesis NR, in which bottom and middle temperature rise were only 5.0°C and 14.1°C, respectively.     

Melting behavior of drawn polypropylene

The melting behavior of drawn, compression-molded isotactic polypropylene has been ex-amined in terms of the infuence of drawing conditions on the observed properties. Two endothermic peaks were observed on differential scanning calorimetry (DSC) for samples when high draw ratios and high heating rates were used during DSC tests. The peak at lower temperature is influenced by draw ratio, temperature, and rate, and exhibits a strong superheating effect. The species associated with this peak can partially recrystallize into another species associated with the peak at higher temprature during DSC measurements. The position of the peak at higher temperature depends only on draw ratio. It is proposed that the doubel-melting peaks at lower and higher temperature result from extremely thin quasi-amorphous or crystalline layers between microfibrils and the lamellar crystals within microfibrils, repectively. © 1993 John Wiley & Sons, Inc.     

Melting behavior of isotactic polystyrene

The melting behavior of isotactic polystyrene, crystallized from the melt and from dilute solutions in trans-decalin, has been studied by differential scanning calorimetry and solubility measurements. The melting curves show 1, 2, or 3 melting endotherms. At large supercooling, crystallization from the melt produces a small melting endotherm just above the crystallization temperature T_c. This peak originates from secondary crystallization of melt trapped within the spherulites. The next melting endotherm is related to the normal primary crystallization process. Its peak temperature increases linearly with T_c, yielding an extrapolated value for the equilibrium melting temperature T_c° of 242 ± 1°C as found before. By self-seeding, crystallization from the melt could be performed at much higher temperature to obtain melting temperatures as high as 243°C, giving rise to doubt about the value of T_c° found by extrapolation. For normal values of T_c and heating rate, an extra endotherm appears on the melting curve. Its peak temperature is the same for both melt-crystallized and solution-crystallized samples, and independent of T_c, but rises with decreasing heating rate. From the effects of heating rate and partial scanning on the ratio of peak areas and of previous heat treatment on dissolution temperature, it is concluded that this peak arises from the second one by continuous melting and recrystallization during the scan.     

Thermal stress development of liquid silicone rubber seal under temperature cycling

Liquid Silicone Rubber (LSR) is commonly used as gasket or seal material in many industrial applications. The temperature dependent material property of polymeric rubbers will result in stress relaxation/creep. The development of compressive stress in LSR between two clamping metal plates under temperature cycling is discussed in this paper. It is found that (a) in addition to stress relaxation, thermal expansion or contraction of the material contributes the most in the observed stress variation during temperature change, and (b) the stiffness of LSR appears to change according to temperature history.     

Shape memory natural rubber

Charles Goodyear discovered the vulcanization of natural rubber (NR) 170 years ago and transferred the gooey natural compound into the first representative of an entirely new class of materials; the elastomers. Thenceforth, NR was intensively explored and was used for countless products to date. All the more surprising, it was found recently that NR exhibits superior and unexpected properties whenever it is cross-linked to a degree smaller than 0.4% which is fairly below the commonly used 1%–2%. This article gives a brief overview on the exceptional properties of lightly cross-linked NR, named shape memory natural rubber (SMNR), including the cold programmable shape memory effect, storing of extremely large strain, energy and cold, and its capability to sense and memorize environmental parameters. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1381–1388     

Effect of molecular orientation on the fracture behavior of carbon black-filled natural rubber compounds

The fracture behavior of carbon black-filled natural rubber compounds, differing in filler content, was studied performing tensile tests in biaxial loading conditions, using a central notched cross-shaped specimen. The test consisted of two steps: a drawing step was initially performed loading the specimen in the direction parallel to the notch plane, up to different draw ratios, and then the specimen was loaded in the direction normal to the notch plane up to fracture. Using a fracture mechanics approach, the fracture toughness was evaluated as a function of the draw ratio applied in the drawing step. A correlation between the fracture phenomenology observed and molecular orientability and orientation was attempted. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1509–1515, 2010     

Measurements of freezing‐point depression to evaluate rubber network structure. Crosslinking of natural rubber with dicumyl peroxide

An experimental approach based on the freezing‐point depression of a solvent in a swollen gel has been developed to characterize the structure of rubber networks. This property depends on the conditions required for the formation of crystalline nuclei, which are limited by the elastomer network restrictions. Information about the functionality, spatial distribution, and number of crosslinks can be obtained by the use of this easy and ready experimental method. Application of the tube model of rubber elasticity in the uniaxial stress–strain experiments of natural rubber samples vulcanized with dicumyl peroxide yields the characteristic parameters of the rubber networks, which are in concordance with the network structures predicted by the freezing point method. Finally influence of vulcanization conditions in network structure and its relationship with the mechanical properties was evaluated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 544–556, 2007     

Photocrosslinking of acrylated natural rubber

Photocrosslinkable elastomers with pendent acrylate groups have been synthesized by ringopening reaction of epoxidized natural rubber with acrylic acid. The kinetics of the acrylation reaction has been studied by infrared spectroscopy and shown to obey a simple first-order law. The acrylated natural rubber undergoes a fast crosslinking-polymerization when it is exposed to UV radiation in the presence of an aryl ketone photoinitiator, with formation of a tridimensional polymer network within a few seconds. The cure kinetics has been studied in real time by monitoring the disappearance of the IR absorption of the grafted acrylate double bond. The rate of polymerization was found to increase linearly with the degree of acrylation of the rubber, reaching values up to 3 mol kg^?1 s^?1. The isoprene double bond, which is inactive in virgin natural rubber, also undergoes polymerization upon UV exposure when epoxy or acrylate groups are present. The UV-cured polymer becomes totally insoluble in the organic solvents and exhibits remarkable mechanical properties, such as hardness, flexibility, and impact resistance. The gel fraction and the hardness were both shown to increase with the degree of acrylation and with the cure extent. © 1993 John Wiley & Sons, Inc.     

Tearing of unvulcanized natural rubber

The tear behavior of unvulcanized natural rubber has been studied by using established techniques normally adopted for the study of vulcanized rubbers. Unvulcanized rubber has been found to tear in a relatively steady manner, in contrast to the stick-slip tear behavior of the vulcanized rubber, the tearing energy being dependent on the rate of tearing. Crystallization seems to be an important factor in determining the tear behavior since it has not been found possible to tear unvulcanized SBR under the same conditions. The effect of the pronounced imperfect elastic nature of the material was studied under conditions where the driving force for tearing was solely governed by the rate of release of elastic energy. Under such conditions, it has been found that the tearing energy is determined not by the strain energy required to stretch the material but by the energy which can be recovered on retraction. The set developed in the test piece, due to imperfect elasticity, has also to be taken into account.