Melt flow and mechanical properties of sulfonated butyl rubber ionomers

Study of melt flow properties and mechanical properties of sulfonated butyl rubber ionomers showed that in the case of lithium ionomers addition of zinc stearate lowered obviously the melt viscosity, represented by torque value of a Brabender rheometer, and enhanced tensile strength of the ionomer up to 25% of zinc stearate, while in the case of ethylamine neutralized ionomer addition of zinc stearate lowered the melt viscosity not so obviously as in the case of lithium ionomer and slightly affected the tensile strength. Amine neutralized ionomers exhibited very low permanent sets, while the lithium ionomer showed much higher permanent set, which increased with sulfonate group and amount of zinc stearate added. Increase of neutralization degree below equivalent ratio of 1 significantly raised the melt viscosity and tensile strength. For monovalent cation ionomer, melt viscosity and tensile strength diminished with decreasing ionic potentials, but for divalent cation ionomers with increasing ionic potentials and with decreasing covalent character tensile strength decreased and melt viscosity increased. For different amine neutralized ionomers tensile strength decreased in the following orders: ethylamine > triethylamine > diethylamine; isopropylamine > ethylamine > tertiary butylamine > methylamine; ethylamine > hexylamine > dodecylamine > octadecylamine.     

New polyisobutylene-based model elastomeric ionomers: RheoLogical behavior

The rheological behavior of sulfonated polyisobutylene based elastomeric ionomers has been studied. The effects of molecular architecture, type of cation, and addition of excess neutralization agent were investigated. The effect of temperature was studied to a limited extent. In a specific case, the influence of an ionic plasticizer, zinc stearate was also examined. It was found that in these telechelic ionomers where the ionic groups are located exclusively at the chain ends, significant Ionic interactions may persist even at 180°C. The zinc-neutralized ionomers had the lowest viscosity as compared to the corresponding potassium- or calcium-neutralized ionomers. The covalent character of zinc is believed responsible for this behavior. Other factors being constant, the triarm based ionomers are more viscous than the monofunctional ionomers. A mixture of monofunctional ionomers with the triarm, species is a model for dangling chain ends, and results in a slight lowering of the viscosity under the conditions studied. Zinc stearate acts as an ionic plasticizer. Upon the addition of 15 percent by weight of zinc-stearate to the ionomer, the low shear rate viscosity drops by several orders of magnitude and renders the ionomer thermally processable at moderate temperatures.     

High‐temperature Bending Strength of Self‐Healing Ni/Al2O3 Nanocomposites

Bending strength of 5 vol.% Ni/Al₂O₃ composites as a function of testing temperature is investigated at temperatures ranging from room temperature to 1200°C. Self‐healing performance at high temperatures of the composites is evaluated by conducting high‐temperature bending tests for as‐sintered, as‐cracked, and as‐healed specimens. Bending strength of as‐sintered specimens dramatically decreases from 995 MPa at room temperature to 205 MPa at 1200°C. Additionally, the plastic deformation of the as‐sintered specimens occurs when the testing temperature reaches to 1200°C. The values of high‐temperature bending strength of as‐healed specimens are comparable with those of as‐sintered specimens. Similar to that of as‐sintered specimens, bending strength of as‐healed specimens degrades when the testing temperature increases. Results of the present study indicate that the recovery of bending strength by the self‐healing function is able to achieve at temperatures as high as 1200°C. Unlike the mechanical behaviors at high temperatures of as‐sintered and as‐healed specimens, the bending strength of as‐cracked specimens slightly increases with the increase of testing temperature. This phenomenon is attributed to the effect of the self‐healing mechanism during high‐temperature bending tests.     

Effects of acid neutralization on the properties of K+ and Na+poly(ethylene-co-methacrylic acid) ionomers

The effects of the degree of neutralization of the acid groups and, to some extent, the precursor melt index on the thermal, rheological, and mechanical properties of two series of poly(ethylene-co-methacrylic acid) (EMAA) ionomers, one based on sodium (Na⁺) cations and one based on potassium cations (K⁺), were examined. Differential scanning calorimetry (DSC) and modulus results indicate that the secondary crystallization of the ionomers is generally completed 21 days after melt processing. DSC results indicate that the extent of crystallization increases with increasing neutralization level. The mechanical relaxation seen by dynamic mechanical analysis (DMA) in the vicinity of the secondary crystal melting point shifts to higher temperatures as the neutralization level increases. The rheological properties increase with decreasing precursor melt index and with increasing neutralization level to a lesser extent. The ionomer modulus and yield strength increase with increasing neutralization level up to 40% neutralization and then plateau or slightly decrease with further neutralization. The plateaus/maxima may be the result of an optimal spacing of alkaline ions and carboxyl groups within ionic groups at neutralization levels near 33%. The elongation at break and the Izod impact strength decrease with increasing neutralization. The modulus, yield stress, and impact strength are generally lowest for the ionomers with the highest precursor melt index.     

从聚苯乙烯大单体—丙烯酸丁酯—丙烯酸三元共聚物中和制得的热塑性弹性体的力学性能

研究了经离子中和的聚苯乙烯大单体与丙烯酸及丙烯酸丁酯共聚物的力学性能,包括中和方法、羧酸含量、中和度、金属离子种类及聚苯乙烯支链的含量及分子量等对力学性能的影响。这种双重物理交联产物的强度为未中和的三元共聚物或经离子中和的丙烯酸—丙烯酸丁醋共聚物的二倍。动态力学谱表明有二个玻璃化温度,呈现微观相分离。     

Evaluation of wood bonding performance of water-washed cottonseed meal-based adhesives with high solid contents and low press temperatures

Water-washed cottonseed meal (WCSM) has been shown as a promising bio-based wood adhesive. In this work, we tested the bonding strength of WCSM slurries with high solid contents and low press temperatures per industrial input for non-structural applications as European Standard Class D1 wood adhesives. Increasing the WCSM content from 11 to 20% and 30% did not substantially change the adhesive strength but increased the viscosity of WCSM slurries dramatically. The shear strength at break of the maple wood pairs bonded at 40 and 60 °C was lower than that of maple pairs bonded at 100 °C. However, the shear strength of the pairs bonded at lower temperatures (40 and 60 °C) could be improved by extending the press time from 20 to 120 min. Addition of citric acid (CA) improved the viscosity of the WCSM adhesive at 20% solid content, but lowered the adhesive strength. The addition of denaturing reagent sodium dodecyl sulfate (SDS) showed reverse impacts on the adhesive strength and viscosity, compared to CA addition. Based on these observations, eight adhesive slurries were formulated with 20 and 30% of WCSM, 3% of CA or SDS, or 9.6% or 19.1% of denaturing reagent guanidine hydrochloride (GdmCl), and their bonding strengths were tested. These formulations could be used as the basis for developing low temperature WCSM-based wood adhesives to meet the criteria of both operational flowability and shear strength of the domestic furniture and small utensils niche markets for forest products.     

Aluminum phosphates as refractory bonds for construction material

Conclusions The density, apparent porosity and bending strength were investigated in specimens with aluminophosphate bonds containing 10 to 50% AlPO₄ and with a 0 to 70% degree of neutralization at temperatures up to 1560 C.Bonds with 20% AlPO₄ exhibited the highest density (at a minimum apparent porosity) and strength (regardless of N and firing temperatures).The possibility of using bonds with N=0 to 70% containing 20% AlPO₄ for the adhesion of metal and ceramics was investigated. The shearing strength of the bond after heat treatment at 500 to 1300 was determined.It was found that the durability of the bond increases at temperatures below 1100 C and declines above that temperature range. The bond in a specimen with N=50% exhibited maximum durability.     

Melt rheology of ion-containing polymers. I. Effect of molecular weight and excess neutralizing agent in model elastomeric sulfonated polyisobutylene-based ionomers

Melt rheology of elastomeric triarm sulfonated polyisobutylene model ionomers has been studied. The molecular weights (M _n) of the polymers have been varied from 8300 to 34,000. The sulfonated materials were neutralized with potassium hydroxide either to the exact stoichiometric equivalence point or to twice this amount, i.e., 100% excess neutralizing agent was added. For comparison one nonsulfonated precursor of M _n = 8300 was also studied. It was observed that the introduction of one sulfonate group at each chain end of the triarm poly-isobutylene molecule changes the state of matter at room temperature. Specifically, the unsulfonated materials are viscous liquids while the sulfonated ionomers are solid elastomers at room temperature. The zero-shear melt viscosity of the unsulfonated precursor is 900 poise (90 Pa·s), at room temperature while for those materials neutralized with potassium hydroxide to the exact stoichiometric point it is above 9 × 10³ poise (900 Pa·s) at 180°C. As expected, the zero shear viscosity increases with an increase in the molecular weight. Significant ionic interactions still persist at 180°C as evident by the high viscosity of the ionomers. However, at higher frequencies (～600 rad/s), the melt viscosity decreases to about 5 × 10³ poise for the different molecular weight materials. The melt viscosity of ionomers containing 100% excess neutralizing agent shows a dramatic increase. The excess KOH is speculated to be incorporated into the ionic domains rather than uniformly distributed throughout the matrix. This results in an increased strength of the ionic aggregates, thereby increasing the melt viscosities. Thus, due to the very pronounced effect on rheological properties it is important to know not only the extent of neutralization (up to full neutralization) but also the amount of excess neutralizing agent, if any, which is present in the sample.     

Heat‐sealing properties of soy protein isolate/polyvinyl alcohol film made compatible by glycerol

Heat‐sealing properties are necessary for packaging materials. Soy protein isolate/polyvinyl alcohol (SPI/PVA) blend film is a biodegradable potential packaging material. We analyzed the effects of PVA content (0–20%), glycerol content (1–3%), and sealing temperature (180–230°C) on the heat‐sealing properties of SPI/PVA blend film. Results showed that SPI/PVA film obtained the desired sealing properties when the PVA content exceeded 15%. The sealing strength increased with the PVA content, reaching a maximum upon blending with 20% PVA and 1% glycerol at 220°C. The temperature at sealing strength was approximately twice that at 180°C. However, glycerol migrated to the surface and hindered the entanglement of macromolecular chains in the sealing interface, thereby resulting in reduction of seal strength. Glycerol vaporization at 204°C led to aesthetically unacceptable blistering in the sealing area. Therefore, the optimum sealing temperature of the blended film was ～200°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40308.     

Preparation,characterization, and some properties of ionomers from a sulfonated styrene–butadiene–styrene triblock copolymer without gelation

The conditions for the sulfonation of a highly unsaturated styrene–butadiene–styrene triblock copolymer (SBS) in cyclohexane containing a small amount of acetone with acetyl sulfate made by sulfuric acid and acetic anhydride without gelation were studied. After neutralization with metallic ions, the ionomers were characterized with IR spectrophotometry, dynamic mechanical analysis, and transmission electron microscopy. The melt flow, solution properties, and mechanical properties of the ionomers were studied. The results showed that gelation occurred during the sulfonation of SBS in cyclohexane at a 5–10% concentration without acetone, whereas in the presence of 5–10 vol % acetone, sulfonation proceeded smoothly without gelation. Transmission electron microphotographs of the lead ionomer indicated the presence of ionic domains. A dynamic mechanical spectrum showed the presence of three transition temperatures: ?82.9, 68, and 96.5°C. The melt viscosity of the ionomer increased with the sulfonate content. The melt viscosity of the different ionomers neutralized with different cations seemed to decrease with decreasing ionic potential for both monovalent cations and divalent cations The solution viscosity of the sodium‐sulfonated ionomer increased with increasing sulfonate content. The ionomer still behaved as a thermoplastic elastomer and showed better mechanical properties than the original SBS. The tensile strength of the different ionomers decreased as follows. For the monovalent cations, it decreased with decreasing ionic potentials: Li⁺ > Na⁺ > K⁺. For the divalent cations, it decreased with increasing ionic potentials: Pb²⁺ > Zn²⁺ > Mg²⁺. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1398–1404, 2005     

Study on a series of main-chain liquid–crystalline ionomers containing sulfonate groups

A series of main-chain liquid–crystalline ionomers containing sulfonate groups pendant on the polymer backbone were synthesized by an interfacial condensation reaction of 4,4′-dihydroxy-α,α′-dimethyl benzalazine, a mesogenic monomer, with brilliant yellow (BY), a sulfonate-containing monomer, and a 1/9 mixture of terephthaloyl and sebacoyl dichloride. The structures of the polymers were characterized by IR and UV spectroscopies. DSC and thermogravimetric analysis were used to measure the thermal properties of those polymers, and the mesogenic properties were characterized by a polarized optical microscope, DSC, and wide-angle X-ray diffraction. The ionomers were thermally stable to about 310 °C. They were thermotropic liquid–crystalline polymers (LCPs) with high mesomorphic-phase transition temperatures and exhibited broad nematic mesogenic regions of 160–170 °C, and they were lyotropic LCPs with willowy leaf-shaped textures in sulfuric acid. However, the thermotropic liquid–crystalline properties were somewhat weakened because the concentration of BY was more than 8%. The inherent viscosity in N-methyl-2-pyrrolidone suggested that intramolecular associations of sulfonate groups occurred at low concentration, and intermolecular associations predominated at higher concentration. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2210–2218, 2001     

The effect of heat sealing temperature on the properties of OPP/CPP heat seal. I. Mechanical properties

The effect of heat sealing temperature on the mechanical properties and morphology of OPP/CPP laminate films was investigated. The laminated films were placed in an impulse type heat sealing machine with both CPP sides facing each other. The temperatures investigated ranged from 100 to 250°C. T‐peel and tensile tests in combination with SEM were used to characterize the heat seals. A minimum seal initiation temperature of 120°C was identified for OPP/CPP laminate heat sealing. Peel strength increased sharply from zero at 110°C to maximum at 120°C, after which a gradual decrease was observed. Tensile strength initially increased until 120°C, after which it gradually decreased until 170°C and assumed a constant value beyond that. The initial rise has been associated to cold crystallization, while the reduction between 120°C and 170°C was due to relaxation in molecular orientation. Beyond 170°C, all the orientation in the laminate has been lost so orientation effects are nullified. Morphological studies with SEM revealed that seals were partially formed at lower temperatures, while the laminates were totally fused together at high temperatures, with intermediate temperatures showing properties that lie in between. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 753–760, 2005     

Anisotropic modeling of isothermal squeezing flow of Glass-Mat reinforced thermoplastics (GMT)

Lubricated isothermal compression molding of Glass-Mat Thermoplastic (GMT) was carried out using a circular mold on a 100 kN test machine to characterize the rheological parameters for squeezing flows of the material. Flow was found to be anisotropic with the main flow direction perpendicular to the main fiber direction. In-plane flow of circular specimens was found to follow an elliptical shape, which allows a relationship to be derived between extensional strain rates in the two main in-plane directions. A transversely isotropic incompressible Newtonian fluid model was successfully applied to interpret the squeezing data parallel and perpendicular to the main flow direction. Longitudinal and transverse extensional viscosities were calculated for two squeezing temperatures, 180°C and 200°C. The results were compared to the standard isotropic power law interpretation, showing the largest anisotropic viscosity to be 20% higher than the isotropic viscosity at low closing speeds and 9.5% higher at fast closing speeds. A very significant difference in the viscosities was found between the two different temperatures as the viscosity at 200°C dropped to about 65% of its value at 180°C. In this work, original material sheets were also confirmed to display anisotropic mechanical properties. The final squeezed specimens were found to have different fiber volume fractions in the same specimen.     

The crystallization and formation of cluster of ethylene ionomer during physical aging

The effect of the physical aging of ethylene ionomers was studied for the samples with the acid content of 5.4 mol%, and the degree of neutralization, 0%, 60% Na, 60% Zn, and 90% Zn. The information about the crystal and the cluster part of the physically aged ionomers was obtained by differential scanning calorimetry and by dynamic viscoelastic measurements, respectively. The degree of crystallinity and the dynamic modulus for the ionomers of the degree of neutralization 0%, 60% Na and 60% Zn increased gradually with the aging time; on the other hand, the crystallinity of 90% Zn remained constant and the modulus at 100°C increased to a certain value up to a period of 100 h, but thereafter the crystallinity increased remarkably and the modulus remained. These facts indicate that the crystallization of neutralized ethylene ionomer starts after clustering and the clustering would finish at early stage of the physical aging for intermediately neutralized ethylene ionomer. The physical aging effect of the ethylene ionomers was, thus, found to be important to material design.     

不同金属离子及胺中和的磺化丁基橡胶离聚体的性能

研究了不同金属离子及胺中和的磺化丁基橡胶离聚体的熔融流动性及力学性能。结果表明,随着硬脂酸锌加入量的增加,锂离聚体的熔融黏度降低,拉伸强度增大;随离聚体中磺酸基含量的增加,锂离聚体的熔融黏度和拉伸强度增大。对于一价金属离子中和的离聚体,其熔融黏度及拉伸强度随着离子电位的降低而减小;对于二价金属离子中和的离聚体,随着离子电位的下降及共价性的增加,熔融黏度下降而拉伸强度增大。用胺中和的离聚体,硬脂酸锌的影响较小,未加硬脂酸锌的离聚体具有较高的扯断伸长率及较低的永久变形,是良好的热塑性弹性体;随离聚体中磺酸基含量的增加,乙胺离聚体的拉伸强度增大。对于不同胺中和的离聚体,其拉伸强度按下列顺序依次降低：乙胺,三乙胺,二乙胺;乙胺,己胺,十二胺,十八胺。     

The effect of curing temperature on thermal,physical and mechanical characteristics of two types of adhesives for aerospace structures

The effects of cure temperatures on the thermal, physical and mechanical characteristics of two types of thermosetting structural epoxy film adhesives were determined in detail. The aim of this paper is to assess the effect of cure temperatures (82–121 °C) on the degree of cure of the two adhesives and the relevant void formations that need to be addressed in bonded part production and repair. Two thermal parameters were used to characterize the advancement of the reaction, such as degree of cure and glass transition temperature. The joint properties with respect to the cure temperatures were characterized by void content and bond-line thickness measurements and lap shear strength tests. Experimental results presented that all lap shear strengths were well within minimum shear strength (29 MPa) required by the specification of the film-type adhesive. However, the lap shear strength testing after aging at 82 °C and 95%R.H for 1000 h showed that the improved durability when the adhesive is cured at 121 °C did not occur for the 82 °C cure. Low curing conversion (75–77% degree of cure) combined with high voids (over 2 areal%) has a catastrophic effect on the bonding qualities at the metal-adhesive interface and due to lack of cohesion in the adhesive. The changes in the interface caused by the low temperature curing may contribute to an increased susceptibility of the bonded joint to moisture and consequent bond-line degradation.     

Asphalt impregnation of high strength mortar and concrete using temperature difference

Asphalt impregnation of steam cured high strength mortar and concrete is studied. The test specimens were dried at 105°C to constant weight and heated to temperatures between 50 and 350°C before impregnation. The impregnation was carried out at atmospheric pressure by dipping the test specimens into heated asphalt bath at 170°C (viscosity 35 cSt).The results showed that the impregnation depth increases with increase in concrete temperature. The highest impregnation depth achieved was at 225°C concrete temperature. The impregnation depth was regular (approximately 10 mm). Water absorption tested (after 7 days under water) was reduced by more than 99%.     

Melt Rheology of Low-Density Polyethylene/Polyamide 6 using Ionomer as a Compatibilizer

Rheology of blends of polyamide 6 with low-density polyethylene compatibilized with sodium-, zinc-, and lithium-neutralized ethylene-methacrylic acid ionomers were investigated at 11, 33 and 55% neutralization of ionomer. Blends of polyamide 6 with low-density polyethylene without compatibilizer had lower shear viscosities than a mixing rule would predict. After adding compatibilizer, the shear viscosity of the blend is increased, presumably due to the formation of graft copolymer from the reaction of the primary amine with free acid groups. The increase of shear and elongational viscosity properties is less with EMAA than with the ionomers; which is consistent with mechanical property and dispersed phase size results presented in an earlier publication. For high polyamide 6 content blends, zinc-neutralized compatibilizers yielded the highest shear and elongational viscosities; while for low polyamide 6 contents, lithium-neutralized compatibilizers yielded the highest viscosities.     

Physicomechanical and dielectric properties of magnesium and barium ionomers based on sulfonated maleated styrene‐ethylene/butylene‐styrene block copolymer

Ionomers, containing both carboxylate and sulfonate anions on the polymer backbone, based on metal cations like Mg⁺² and Ba⁺² were prepared by sulfonating maleated styrene‐ethylene/butylene‐styrene block copolymer, hereafter referred to as m‐SEBS, followed by its neutralization by metal acetates. Infrared spectroscopic studies reveal that sulfonation reaction takes place in the para position of the benzene rings of polystyrene blocks and metal salts are formed on neutralization of the precursor acids. Dynamic mechanical thermal analyses show that sulfonation causes increase in T_g of the rubbery phase of m‐SEBS and decrease in tan δ at T_g of the hard phase, along with formation of a rubbery plateau. The changes become more pronounced on neutralization of the sulfonated maleated SEBS, and the effect is greater in the case of Ba salt. Dielectric thermal analyses (DETA) show that incorporation of ionic groups causes profound changes in the dielectric constant (ϵ′) of m‐SEBS. In addition to the low temperature glass–rubber transition, the plot of ϵ′ vs. temperature shows occurrence of a high‐temperature transition, also known as the ionic transition. Activation energy for the dielectric relaxation could be determined on the basis of frequency dependence of the ionic transition temperature. Two values of the activation energy for the dielectric relaxation refer to the presence of two types of ionic aggregates, namely multiplets and clusters. Incorporation of the ionic groups causes enhancement in stress–strain properties as well as retention of the properties at elevated temperatures (50° and 75°C), and the effect is more pronounced in the case of Ba ionomer. Although sulfonated ionomers show greater strength than the carboxylated ionomers, the sulfonated maleated ionomers show higher stress–strain properties in comparison to both sulfonated and carboxylated ionomers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 816–825, 2000