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.     

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.     

Cold-rolling of polymer: 4. Toughness enhancement in amorphous polymers

Several types of amorphous polymers have been cold-rolled to various thickness reductions and the notched Izod impact behavior has then been studied. It has been determined that whereas some polymers exhibit large increases in impact strength with modest reductions in thickness other polymers only exhibit small increases in impact strength. For example, PVC, ABS, poly (phenylene oxide), and polysulfones show large increases in impact strength whereas rubber-toughened acrylics show only a small increase in impact strength.     

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.     

Fabrication of high modulus films by solid state rolling

Solid state rolling of semicrystalline polymers represents a high speed process for producing oriented, high modulus films, tapes, and sheets. The important process variables include roll temperature, thickness of initial sheet, roll speed, take-up tension, roll diameter, and initial morphological state of the polymer. Roll temperature controls both the extent of maximum deformation and the rate of rolling. A minimum temperature exists for each polymer below which the orientation process is sharply limited. This condition is similar to the limitation present in the hydrostatic extrusion process, in which the alpha crystallization temperature limits the orientation process. Roll speeds as high as 20 m/min have been realized. It is apparent that film thickness and thickness reduction ratio have a strong effect on the ultimate rolling rate. The process, as currently practiced, is adiabatic, and therefore, heat transfer limited. The take-up tension influences the extant of orientation in the amorphous phse of of the polymer. This in turn affects its thermal and chemical stability. The effect of roll diameter is to limit the extent of thickness reduction by causing roll-film slippage when the roll dianmeter to thickness reduction ratio is below some as yet undetermined value. The initial morphological state of the polymer affects the amount of crystalline deformation possible, the surface texture of the rolled film, and the tear resistant of the oriented film.     

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. 1 Influence of rolling on properties of amorphous polymer

Strips of ductile, amorphous thermoplastic polymers such as polycarbonates, acrylonitrile-butadiene-styrenes, polysulfones and polyphenylene oxides have been reduced in thickness by passing them through a metalworking rolling mill at room temperature. Properties of the rolled strips were studied as a function of the thickness reduction. In addition to rolling unidirectionally, cross rolling (biaxial rolling) was also studied using equal thickness reductions in each direction. The maximum thickness reduction (t_o — t_f)100/t_o which could be achieved was approximately 60 per cent regardless of the polymer studied here. Stress-strain curves, density changes, thermal stability, hardness and Izod impact strengths have been determined as a function of thickness reduction and sheet direction.     

The relationship between mechanical properties and structure in rolled polypropylene

The relationship between mechanical properties and fine structure has been studied in polypropylene rolled both unidirectionally and biaxially (cross rolled). In unidirectionally rolled samples, a complex dependence with cold work is observed with a substantial change being observed at about 50 percent cold work. At 70 percent cold work, the yield strength and tensile strength increase substantially in the roll direction as compared with the starting billet but decrease only slightly in the transverse direction. Above 50 percent cold work, Young's modulus increases rapidly in the roll direction with a smaller increase in the transverse direction. The elongation to freak decreases in the roll direction but increases in the transverse direction. A striking feature is the large increase in ductility due to a small amount of cold work (ca., 10-20 percent). Analogous property changes are observed for cross rolled samples although no significant variation with direction in the sheet was found. The complex property changes are accompanied by complex changes in the molecular orientation as observed by wide angle X-ray pole figures and by changes in the morphology as observed with small angle x-ray scattering. These changes are interpreted in terms of a model incorporating tilting both of lamellae and of chain stems within the lamellae at early stages of rolling followed by breakup of lamellae and molecular rearrangement at later stages.     

Impact strength of polymers. 3: The effect of annealing on cold worked polycarbonates

Cold working (rolling) of polycarbonates introduces residual stresses and molecular orientation both of which can improve, the notched Izod impact value. Annealing relieves both residual stresses and orientation. Annealing for various time periods established the critical level of residual stress necessary for the ductile failure mode of polycarbonate in the Izod impact test. The relaxation of both residual stress and molecular orientation was measured as a function of annealing temperature, for annealing times of 2 hs, and the relative changes have thus been determined. It is shown that residual stresses cannot be entirely removed without significantly influencing orientation for 2 h annealing times.     

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.     

Measurement and modelling of the film casting process: 2. Temperature distribution along draw direction

In the case film process a polymer melt is extruded through a slit die, stretched in air and cooled on a chill roll. During the path in air the melt cools and a reduction of both thickness and width takes place; obviously, temperature distribution, thickness and width reductions are function of draw ratio and stretching distance.Temperature distribution along the draw direction was measured as function of flow rate during film casting experiments performed with an iPP resin. A non-contacting method of measurement, based on a narrow-band IR pyrometer, was adopted.A good qualitative agreement is shown between experimental temperature data and predictions of a model accounting of radiation emissivity dependence upon film thickness. Differences are consistent with discrepancies of film thickness evolution along draw direction, indeed the model slightly over predicts both film thickness reduction and, parallel, temperature decrease along the draw direction.     

Super polyolefin blends achieved via dynamic packing injection molding: Tensile strength

The tensile strength of some polyolefin blends, HDPE/PP, HDPE/LDPE, HDPE/ LLDPE, and PP/LLDPE, achieved by dynamic packing injection molding have been investigated as a function of composition and melt temperature. Molecular architecture and phase behavior play an important role in chain orientation, hence the tensile strength. For HDPE, which has a linear structure, the highest enhancement of tensile strength is obtained. LDPE, which has a highly branched structure, the smallest enhancement is seen. PP and LLDPE lie in between. Super polyolefin blends with high tensile strength and high elongation have been obtained by this method. The shear‐induced morphologies with core in the center, oriented zone surrounding the core and skin layer were observed in the cross‐section areas of the samples. The tensile strength was found to be directly proportional to the area of the oriented zone. When the area of oriented zone is less than 35%, the tensile strength is not only the orientation dependency but the blending components dependency as well. When the area of oriented zone is more than 35%, however, our new finding is that the orientation will be the dominating parameter to determine the tensile strength of the blends, independent of the components, the composition, molecular architecture, phase behavior, and crystal morphology. The maximum tensile strength for all the polyolefin blends is extrapolated as to 230MPa, as the area of oriented zone reaches to 100%. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 236–243, 2002     

Analysis of molecular orientation and internal stresses in extruded plastic sheets

The development of molecular orientation and internal stresses in extruded sheet made of polypropylene was analyzed, and their correlations to operating conditions such as draw ratio, cooling rate, die temperature, melt temperature, and die gap opening were studied. Measurements of attenuated-total-reflectance infrared dichroic ratio for the surface molecular orientation, birefringence for the orientation stress distribution in the thickness direction, and free shrinkage ratio for the overall frozen-in stresses were carried out to determine the amount of orientation stresses in the extruded samples. As expected, the overall orientation stress depends strongly on draw ratio, while higher melt temperature reduces the overall orientation. It was found that faster cooling rates and lower die temperatures cause surface orientation stresses to increase as the core orientation stresses remain almost unchanged.     

The preparation and tensile properties of polyethylene composites

Single polymer composites have been prepared using different morphologies of polyethylene as matrix and as the reinforcement. Depending on annealing conditions, the ultraoriented fibers used as reinforcement can have higher melting points (ca. 139°C) than the matrix made from the same conventionally crystallized high-density polyethylene (ca. 132°C) or from low-density polyethylene (ca. 110°C). The optimum temperature has been assessed for bonding to occur by growth of transcrystalline regions from the melt matrix without considerable modulus reduction of the annealed ultraoriented and reinforcement fiber or film. Pullout tests have been used for determining the interfacial shear strength of these single polymer composites. The interfacial shear strength for the high-density polyethylene films embedded in a low-density polyethylene matrix is 7.5 MPa and for high-density polyethylene self-composites is 17 MPa. These values are greater than the strength for glass-reinforced resins. The strength is mainly due to the unique epitaxial bonding which gives greater adhesion than the compressive and radial stresses arising from the differential shrinkage of matrix and reinforcement. The tensile modulus of composites prepared from uniaxial and continuous high-density polyethylene films embedded in low-density polyethylene obeys the simple law of mixtures and the reinforced low-density polyethylene modulus is increased by a factor of 10. High strength cross-ply high-density-polyethylene—low-density-polyethylene laminates have also been prepared and the mechanical properties have been studied as the film orientation is varied with respect to the tensile axis.     

Orientation of polyoxymethylene by rolling with side constraints

In this paper, we describe the application of the constrained rolling process to produce highly oriented polyacetal bars with enhanced mechanical properties. In this process, the heated polymer billet is deformed in a channel formed in the circumference of the bottom roll that provides lateral constraint to the material as it deforms. It is a process that has attracted interest due to its capability to produce thick cross-sectional oriented products continuously and at moderate production speeds. Here the focus is on two commercial grades of polyoxymethylene (a) Delrin^® 100 and (b) Tarnoform^® 300. Tarnoform^®, unlike Delrin^®, is a copolymer. The compression behaviour of these grades has been investigated in a plane strain channel die to determine the optimum constrained rolling conditions. Samples were then rolled to different reduction ratios close to but below the crystalline melting temperature of the two grades.The modulus and strength increased almost linearly with reduction ratio. Rolled Delrin^® exhibited higher modulus and strength than Tarnoform^®. Under impact loading, with the initial notch perpendicular to the rolling direction, the fracture process was incomplete for both resins with the specimens exhibiting a hinge type break. Structural investigations of the rolled samples were carried out by wide and small angle X-ray diffraction. The structures produced were very similar to those produced in plane strain compression test. The pole figures from the (100) reflection suggest that the c axes of the POM crystals are oriented along the rolling direction while ab planes showed clustering of orientation of (100) normals in six directions. SAXS patterns from the rolled samples with the X-ray beam parallel to the force direction showed two-point patterns that suggest the transformation of the spherulitic morphology to a fibrillar structure in this direction. However, perpendicular to the rolling direction, four-point patterns were obtained that suggest cooperative kinking of the lamellae during deformation to produce a chevron-like structure. The enhancement in properties as a result of molecular orientation suggests that these materials can have major commercial applications.     

Role of slippage in the orientation stretch of Oksalon yarns

Conclusions It has been shown that in the continuous orientation stretching of Oksalon yarn in air, the deformation region is located close to the first stretch roll, including an arc of yarn slippage on it.The need to take the slippage arc into account in continuous yarn stretching has been demonstrated.By varying the frictional parameters of the first stretch roll, it is possible to achieve an increase in the strength of the finished yarn.Translated from Khimicheskie Volokna, No. 5, pp. 22–23, September–October, 1985.     

Vortex flow of dilute polymer solutions

It has been observed that very d longchain polymers which are effective in turbulent drag reduction inhibit the formation of a vortex or air core as water drains from a tank. This paper considers the fluid mechanical velocity profile measurements have been performed. There appear to be at least two distinct mechanisms for the vortex inhibition—one involving the viscosity enhancement caused by polymer addition, and the other related to the viscoelastic properties of the polymer solutions. This second mechanism is shown to arise due to the generation of high normal stresses as the air core begins to form. The very close correlation between vortex inhibition and turbulent drag reduction suggests that normal stresses may also play an important role in this latter phenomenon.     

Analysis and evaluation of bondline thickness effects on failure load in adhesively bonded structures

It is well known that adhesive joints have their optimum strength for thin bondline thicknesses (0.1-0.5 mm). The most common analytical methods used for adhesive joint analysis show an improved strength with increasing bondline thickness. This erroneous trend in prediction is investigated in this article. It is found that the through-the-thickness stress distribution in the adhesive is the main cause for the errors. The stresses, both peel and shear, at the interface between the adhesive and the adherend are found to increase, after an initial decrease in the low bondline thickness range, with increasing bondline thickness while the average stresses decrease. This trend explains the trends found in experiments. Further, as experimental results have shown, a theoretical optimum bondline thickness is found.     

Effect of the Quenching Temperature on the Fields of Thermal Stresses and on the Mechanical and Thermal Properties of PMMA

This study explores the photoelasticimetry as a means to investigate factors affecting the residual stresses, particularly the thermal stresses, in polymethyl methacrylate (PMMA). The aim was to study the effect of quenching temperature in three different media: air, water, and ethylene glycol, on the impact strength and thermal properties of PMMA. These temperatures varied from a fixed value of 120°C to various values below Tg and the fields of distribution of cooling stresses have been obtained using a charge-coupled device (CCD) camera. It was observed that the quenching in water at 20°C gives rise to an important density of tensile stresses. However, in the ethylene glycol at 110°C this density has a tendency to disappear. An approximate evaluation of these stresses in a point near the specimen center has been assessed, and it was found that the distribution profile of the fields of tensile stresses was much closer to a parabolic form. Notched Izod impact strength and heat deflection temperature (HDT) were measured, and were found to be particularly sensitive to thermal stresses.     

Poly(p-phenylene terephthalamide) films formed from extrusion and coagulation of liquid crystalline sulphuric acid solutions: Characterization of orientation and void structure,annealing, and upgrading of film mechanical properties

Poly(p-phenylene terephthalamide) (PPD-T) films have been prepared by continuous extrusion of liquid crystalline 17 percent PPD-T/sulphuric acid solutions through an annular die followed by coagulation, Films extruded without drawdown exhibit some polymer chain orientation in the machine direction. This is increased by uniaxially drawing down films. Films produced with a lubricated conical mandrel sitting between the die and the coagulation bath exhibit an equal biaxial orientation. The uniaxially oriented films exhibit highly anisotropic mechanical properties, while the mandrel-produced film exhibits balanced properties. Heat treatment at 350°C results in significant enhancement of the tensile strength of the mandrel film. Void structures in the films have been investigated by mass density, scanning electron microscopy (SEM), and small-angle X-ray scattering (SAXS). Density measurement indicate a void content decreasing with decreasing film thickness and heat treatment. SEM locates micron-size voids in the thickest films, apparently caused by rapid coagulation. SAXS indicates much smaller void sixes which are roughly prolate ellipsoids (long axis in machine direction) for uniaxial films and oblate ellipsoids (short axis in thickness direction) for the mandrel produced films. Various techniques are used to estimate mean void size.