Polymer property enhancement by solid-state forming

The alteration of the physical properties of a polymer by the use of forming techniques which are applied below the melt or glass transition temperature of the polymer has been discussed. The influence of cold rolling (rolling accomplished at room temperature) on the mechanical properties of amorphous polymers was first briefly reviewed (1). The specific effect of rolling on the toughness of polycarbonates, as measured by notched Izod impact strength, was discussed in detail and is summarized in (2). The role of crystallinity in further enhancing the mechanical properties of polycarbonate and the combined effect of rolling and crystallinity was also described and is discussed in more detail in (3). Other amorphous polymers were also discussed, particularly the effect of rolling on the notched Izod impact strength (4). For most polymers studied, a large increase in impact strength occurs for small reductions in thickness and a maximum occurs at a given thickness reduction beyond which the ductility of the material is exhausted. The increase in impact strength is not only a result of molecular orientation but also a function of residual stress placed in the sheet by the rolling process. In addition to the studies on amorphous polymers, recent studies (5, 6) were described on the high-pressure nonisothermal compression molding of linear polyethylenes. Mold pressures up to 80,000 psi were used and several different polyethylenes having various molecular weights (up to 10⁶) were investigated. It was shown that the modulus of elasticity of polyethylene can be increased by a factor of two when the mold pressure is increased to 80,000 psi. A detailed discussion of the changes in morphology responsible for this increased stiffness is presented in (6).     

Cold rolling of polymers 2. Toughness enhancement in amorphous polycarbonates

The effect of cold rolling on the Izod impact strength of amorphous polycarbonates has been studied. The impact strength is a function of the roll reduction as well as the original sheet thickness. Sheets varying from 0.125 to 0.645 inches in thickness have been studied and roll reductions up to 50 percent have been utilized. It is shown that enhancement in impact strength occurs at very small percent roll reductions. The orientation release stress has been measured as a function of roll reduction and the internal stresses through the thickness of the sheets have been studied by birefringence methods. It is suggested that the residual stresses are responsible for impact enhancement rather than the molecular orientation.     

Impact strength of polymers: 1. The effect of thermal treatment and residual stress

The effect of thermal annealing and quenching on the notched Izod impact strength of several polymers has been studied. Primary emphasis was placed on polycarbonate, but ABS, PVC, polysulfone, and polymethylmethacrylate were also studied. It was determined that residual stresses created by thermal quenching from above the glass transition temperature can have a great effect on impact strength for the polycarbonate, PVC, and polysulfone polymers studied. In fact, it is shown that the thickness transition observed in impact strength for polycarbonates is governed by the residual stresses and not by thickness. In polycarbonates, quenched sheets up to 3/8 in. in thickness have shown impact strengths of 18 ft-lb/in. whereas sheets 1/8 in. in thickness can be embrittled by annealing, showing an impact strength of 2 ft-lb/in. However, it has been shown that this embrittlement results from the absence of residual stress. Residual stresses having maximum values up to 3000 psi (in Compression) have been determined at the polycarbonate sheet surface using birefringence measurement techniques. The existence of these compressive stresses is postulated to restrict the extent of craze growth at the notch tip, and the impact specimen can yield rather than fail in a brittle manner if the stress state is sufficient.     

Use of novel polyetheralkanolamine comb polymers as pigment dispersants for aqueous coating systems

The adsorption of a series of polyetheralkanolamine comb polymers characterized by a different length of the hydrophilic tail has been investigated at the carbon black/water interface by measuring adsorption isotherm, contact angle, wetting rate, zeta potential, and particle size distribution. Zeta potential measurements and adsorption layer thickness results suggest that polyetheralkanolamines with high ethylene oxide (EO) content provide only steric stabilization and they adsorb at the interface with the ethylene oxide chains in a coil conformation. The thickness of the adsorbed layer increases with increasing EO units; however, the surface tension and interfacial tension decrease with increasing EO content. Adsorption isotherms show that most of the added polyetheralkanolamine adsorbs onto the carbon black and only a small amount stays in the water phase. When treated with a polyetheralkanolamine, carbon black dispersions show uniform (unimodal) and narrow particle size distribution with very small median sizes of about 0.10 μm. The pigment concentrates containing the polyetheralkanolamine show excellent color compatibility in various decorative commercial white paints containing a wide range of resins and exhibit low viscosity with nearly Newtonian flow behavior. Presented at the 2006 FutureCoat! Conference, sponsored by the Federation of Societies for Coatings Technology, in New Orleans, LA, on November 1–3, 2006.     

Thermoplastic matrix sheet composites

Until recently, most high performance composites have been made with low-viscosity thermosetting polymers. These polymers are ideally suited for producing composites in low production quantities because a wide variety of custom shapes can be manufactured without a high degree of mechanization. As the demand for composites increases, there is a need to develop high-volume production techniques. Thermoplastic polymer-based composites are better suited to high-volume production than thermoset-based composites because only heat and pressure are needed to form parts; no chemical reaction is required. Thermoplastic matrix composites are not well suited for low-volume production runs because the need to handle high temperatures and pressures demands equipment that is best utilized for large production runs. In addition to processing advantages, thermoplastic matrix composites exhibit improved impact strength and chemical resistance over most thermoset-based composites. In the course of this work, composites reinforced with long and continuous glass fibers were produced that had tensile strengths as high as 270 MPa, tensile moduli of 16.2 GPa, and notched Izod impact strengths of 11.1 J/cm.     

Nucleation of microcellular foam: Theory and practice

Microcellular polymer foams exhibit greatly improved mechanical properties as compared to standard foams due to the formers' small bubble size. Microcellular foams have bubbles with diameters on the order of 10 microns, volume reductions of 30 to 40 percent, and six or seven times the impact strength of solid parts. They are produced through the use of thermodynamic instabilities without the use of foaming agents. This method leads to a very uniform cell size throughout a part's cross section. A theoretical model for the nucleation of microcellular foams in thermoplastic polymers has been developed and experimentally confirmed. This model explains the effect of various additives and processing conditions on the number of bubbles nucleated. At levels of secondary constituents below their solubility limits, an increase in the concentration of the additive or the concentration of gas in solution with the polymer increases the number of bubbles nucleated. Nucleation in this region is homogeneous. Above the solubility limit of additives, nucleation is heterogeneous and takes place at the interface between second phase inclusions and the polymer. The number of bubbles nucleated is dependent on the concentration of heterogeneous nucleation sites and their relative effect on the activation energy barrier to nucleation. In the vicinity of the solubility limit, the two mechanisms compete.     

Impact strength of polymers 2: The effect of cold working and residual stress in polycarbonates

The influence of cold working on the toughness improvement in glassy amorphous polycarbonates was studied. Cold working processes, namely rolling and. Steckel rolling were used to produce thickness reductions up to 40 percent in flat-strip specimens. The notched Izod impact strength and tensile properties were measured as a function of strip thickness reduction. It was shown that the toughness enhancement in polycarbonates cold worked to low thickness reductions was due to the residual stress state present as opposed to molecular orientation which becomes significant at higher degrees of cold work. Residual stress measurements were made by using the layer removal technique. Residual tensile stresses as high as 2100 psi were present in 1/4-in. cold-rolled polycarbonate at the surface. The maximum stress in the center of the specimen was 1100 psi in compression. The residual stresses at the surface decreased with increasing thickness reduction. The residual stress state for Steckel rolled. 1/2-in. polycarbonate was also measured and found to be more complex than for the thinner samples, The results demonstrated that surface tensile stresses and interior compressive stresses can produce large values of impact strength if the notch is to be machined after cold working. Thus, the values of impact strength measured from the notch Izod specimen are sensitive to the residual stress state in the polymer. This behavior is in contrast to earlier studies on thermally quenched material in which the material was quenched after notching. The thermal quenching produced surface compressive stresses which were also present at the notch tip. The presence of compressive residual stresses at the center of the notch suppressed the formation of a craze leading to toughness enhancement in cold worked polycarbonate strips. It is shown that by control of residual stresses in polycarbonate, strips at least 1/2 in. in thickness can be made to exhibit ductile failure in the notched Izod impact test.     

Synthesis and characterization of cast resin based on different saturation epoxidized soybean oil

Acrylated epoxidized soybean oils (AESOs) with different level of saturation were obtained by the ring opening of different saturation epoxidized soybean oils using acrylic acid as the ring opener. AESO‐based thermosets have been synthesized by free radical polymerization of these AESOs and methyl methacrylate. The thermal properties of these resins were studied by differential scanning calorimetry and thermo‐gravimetric analysis. The results indicated that the thermal stability of these resins depends upon the epoxy value; the glass transition temperature increases with increasing of epoxy value. The tensile and impact strength of the resins were also studied, and indicated that tensile strength increases with increasing epoxy value, whereas impact strength decreases. The resulting thermosets ranged from elastomers to glassy polymers.     

On the graft polymerization of styrene and acrylonitrile onto polybutadiene in the presence of vinyl acetate. II. Properties of graft polymers

The properties of the graft polymers of styrene, acrylonitrile, and vinyl acetate onto polybutadiene rubber that were prepared for the modification of graft polymers of styrene and acrylonitrile onto polybutadiene (ABS polymers) by emulsion polymerization up to a high degree of conversion have been studied and discussed. Both the impact strength and notched impact strength of the graft polymers have been found to remarkably increase with a rising quantity of vinyl acetate, in particular, in the case of styrene substitution, whereas in the case of acrylonitrile substitution by vinyl acetate, the two characteristics become noticeably poorer. The effects of the vinyl acetate amount and the type of substituted monomers on bending strength, tensile strength, Vicat softening point, and glass transition temperature of the graft polymers are also clearly different. Furthermore, the properties of the above graft polymers blended with styrene/acrylonitrile copolymers have been studied.     

Deep drawability of biaxially rolled thermoplastic sheets

The deep drawability of biaxially cold-rolled thermoplastic sheets has been studied using polycarbonate, polyvinyl chloride, and acrylonitrile-butadiene-styrene polymers. Each polymer was rolled to two different reductions in thickness. The deep drawability of these rolled sheets was measured by determining the limiting draw ratio using a Swift cup test. Strain ratios were measured in three directions for each of the rolled sheets in order to determine the normal and planar anisotropy of the sheets. It has been determined that the drawability of a sheet can be correlated with the normal anisotropy of the sheet and it is the increase in normal anisotropy of a sheet which increases the drawability of the sheet. It has also been shown that lubrication increases the drawability due to a reduction in punch force.     

The influence of residual stresses and orientation on the properties of amorphous polymers

The effect of cold rolling on impact strength of poly(vinyl chloride) (PVC) acrylonitrile-butadiene-styrene (ABS), and an alloy of ABS and polycarbonate (Cycoloy) was studied. The results were presented in terms of Izod impact strength and present oil thickness reduction. The residual stresses molecule orientation and modification of mechanical properties due cold rolling were measured. It was shown that the mechanism of toughness enhancement in PVC, ABS, and Cycoloy different than the one observed in rolled polycarbonates. In the case of a highly localized failure initiation event (a single eraxe), which appears to be present in polycarbonate, the influence of residual stresses, is great, whereas in rubber modified polymers having multiple erasing over a large volume, orientation is more important than residual stress. Hot rolling of poly(methyl methaerylate) holds promise for a continuous process to achieve orientation and toughness enhancement.     

Comparative study of warpage,global shrinkage,residual stresses,and mechanical behavior of rotationally molded parts produced from different polymers

A comparative study of warpage, global shrinkage, and residual quench stresses developed in rotational molding is made for a series of thermoplastics including various polythylenes, polypropylene, polyamide-6, polycarbonate, and polystyrene. The influence of rate of quench on uniaxial stress strain and impact behavior of rotomolded parts was also studied. Generally, warpage, global shrinkage, and residual stresses increase with increasing quench rate for all the polymers. Further, the levels of warpage and global shrinkage increases with extent of crystallization, i.e., products from glassy polymers exhibit little warpage and those from highly crystalline polymers are highly warped. Increasing rate of quench tends to increase elongation to break and impact strength.     

Adhesion Studies of Fluoropolymers

A comparative study of the treatment of polytetrafluoroethylene (PTFE) and poly(vinyl fluoride) (PVF) with “Tetra-Etch” has been carried out. The treatment of PTFE resulted in extensive changes in surface chemistry and topography, whereas with PVF there was no significant change in topography and the chemical changes were much less marked. However, treatment of both polymers resulted in large increases in bond strength.

Multiple bonding experiments in which samples are repeatedly fractured and re-bonded were carried out with untreated PTFE and PVF. These resulted in moderate increases in bond strength with PTFE and large increases with PVF. The results indicate that weak boundary layer (WBL) removal is a key element in adhesion improvement by “Tetra-Etch” on PVF. With PTFE, WBL removal also improves adhesion, but the chemical and/or topographical changes introduced by the “Tetra-Etch” are required for optimum performance.     

Associations between a hydrophobically modified,degradable, poly(malic acid) and a β‐cyclodextrin polymer in solution

A new associating system has been elaborated from mixing a degradable polymer, poly(β‐malic acid‐co‐β‐ethyladamantyl malate), and a β‐cyclodextrin polymer in aqueous solution. Viscosity and dynamic light scattering measurements have been made on solutions of the single copolyester and of mixtures of both polymers. Studies on copolyesters with different percentages of hydrophobic groups (0–7.5%) show that a small proportion of the chains (less than 5% in weight) are aggregated in large structures (100 nm) which dominate the scattering intensity. The mixtures exhibit slow diffusive relaxation modes which correlate with a large viscosity enhancement at low concentration. These effects, which depend sensitively on pH, are attributed to the presence of polydisperse complexes of copolyester and β‐cyclodextrin polymer. The influence of pH, ionic strength, medium composition, and concentration were examined on the mixture of copolymers. It was found that the association properties are controlled by the net charge on the amphiphilic copolyester. © 2001 Society of Chemical Industry     

Polyurethane elastomers based on molecular weight advanced poly(ethylene ether carbonate) polyols. III. Effects of diisocyanate modified diols

A series of diisocyanate-modified, molecular weight advanced poly(ethylene ether carbonate) diols has been prepared, characterized, and formulated into polyurethane elastomers using a prepolymer process. Properties were compared to a polyurethane elastomer control in which the only variable was the diisocyanate modification. The diisocyanate modification produces polymers with increased modulus (445–730% at 25°C), improved tensile strength and hardness properties and reduced (improved) coefficients of linear thermal expansion, while still passing the notched Izod impact test. The tensile strength at break increases with increasing number of urethane moieties in the soft segment and the elongation at break also increases. The plaques studied appear to have a three-phase morphology—a soft segment continuous phase containing amorphous hard segment, an amorphous hard segment phase plasticized by about 11% of the soft segment material, and a crystalline hard segment. The polymers based on the diisocyanate modified polyols are significantly more phase mixed than the control due to the increased amount of hard segment-soft segment interactions taking place. The improved properties of the polymers made with the modified polyols are due to their higher hydrogen bonding protential which gives more physically crosslinked polymers.     

Adhesion Studies of Fluoropolymers

A comparative study of the treatment of polytetrafluoroethylene (PTFE) and poly(vinyl fluoride) (PVF) with “Tetra-Etch” has been carried out. The treatment of PTFE resulted in extensive changes in surface chemistry and topography, whereas with PVF there was no significant change in topography and the chemical changes were much less marked. However, treatment of both polymers resulted in large increases in bond strength.

Multiple bonding experiments in which samples are repeatedly fractured and re-bonded were carried out with untreated PTFE and PVF. These resulted in moderate increases in bond strength with PTFE and large increases with PVF. The results indicate that weak boundary layer (WBL) removal is a key element in adhesion improvement by “Tetra-Etch” on PVF. With PTFE, WBL removal also improves adhesion, but the chemical and/or topographical changes introduced by the “Tetra-Etch” are required for optimum performance.     

Notch sensitivity of polycarbonate and toughened polycarbonate

Notch sensitivity, the effect of a notch radius on the impact behavior of polycarbonate and rubber‐toughened polycarbonate, is investigated by using a model based on the slip‐lines field theory. Impact strength, determined by the Charpy impact test, was found to increase drastically with an increasing notch radius for pure polycarbonate, whereas the increase of impact strength with increased notch radius was not as extreme for rubber‐toughened polycarbonate. These results indicate that the inclusion of rubber particles reduces notch sensitivity. An examination of fracture surfaces reveals that cracks were initiated by internal crazing at some distance from the notch tip for specimens with blunt notches. For pure polycarbonate, the impact strength is found to have a linear relationship with the square of the notch radius, which is in good agreement with that predicted by the proposed model. However, for rubber‐toughened polycarbonate, the linear relationship broke down as the notch radius increased due to the enhanced toughening effect. The proposed model can be applied to clearly explain the notch sensitivity of ductile polymers which exhibit large plastic yielding around the notch tip. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3115–3121, 2003     

聚碳酸酯注射成型制品力学性能的Taguchi分析

采用Taguchi分析方法考察了注射成型工艺参数对聚碳酸酯(PC)力学性能的影响。结果表明,注射成型工艺参数对PC的拉伸强度影响较大,对弯曲强度和冲击强度影响较小;方差分析结果表明,模具温度对拉伸强度的影响最大,注射压力和冷却时间次之,熔体温度的影响最小;模具温度降低,熔体冷却固化层厚度增加,取向程度增大,拉伸强度增加;同时结果表明Taguchi分析方法可以准确地对优选出的成型工艺制备的PC试样的拉伸强度进行预测,其预测值与测量值的偏差仅为0.75%。     

Impact specific essential work of fracture of compatibilized polyamide‐6 (PA6)/poly(phenylene ether) (PPE) blends

The essential work of fracture (EWF) method has aroused great interest and has been used to characterize the fracture toughness for a range of ductile metals, polymers and composites. In the plastics industry, for purposes of practical design and ranking of candidate materials, it is important to evaluate the impact essential work of fracture at high‐rate testing of polymers and polymer blends. In this paper, the EWF method has been utilized to determine the high‐rate specific essential fracture work, w_e, for elastomer‐modified PA6/PPE/SMA (50/50/5) blends by notched Charpy tests. It is found that w_e increases with testing temperature and elastomer content for a given specimen thickness. Morphologically, there are two failure mechanisms: shear yielding and pullout of second phase dispersed particles. Shear yielding is dominant in ductile fracture, whereas particle pullout is predominant in brittle fracture.     

High modulus semi-crystalline polymers by solid state rolling

Solid state rolling of semi-crystalline polymers is shown to be an effective method of producing high strength, high modulus tape at acceptable production rates. High density polyethylene tape was produced having a tensile strength exceeding 300 MPa and a tensile modulus of 8.7 GPa at production rates exceeding 8 m/min. A significant factor in producing highly oriented tape by the rolling process is roll temperature. Increasing the roll temperature from 25°C to 125°C not only increases the maximum extent of orientation achievable, but increases the mechanical properties at a given degree of thickness reduction. Internal frictional heat development limited the maximum thickness reduction ratio of polypropylene to 6.6:1. This reduction was reached by rolling at 150°C. The resultant tape had a tensile modulus of 5.1 GPa and a tensile strength of 300 MPa.