Creep and shrinkage behavior of improved ultrathin polymeric films

Long‐term creep‐deformation and shrinkage characteristics of improved ultrathin polymeric films for magnetic tapes are presented. These films include poly(ethylene terephthalate) (PET), poly(ethylene naphthalate) (PEN), and aromatic polyamide (ARAMID). PET film is currently the standard substrate used for magnetic tapes, and thinner tensilized‐type PET, PEN, and ARAMID have recently been used as alternate substrates with improved material properties. The thickness of the films ranges from 6.2 to 4.8 μm. More dimensional stability is required for advanced magnetic tapes, and the study of creep and shrinkage behavior is important for estimating the dimensional stability. Creep measurements were performed on all available substrates at 25, 40, and 55°C for 100 h. Based on these data, master curves were generated using time–temperature superposition to predict dimensional stability after several years. The amount of creep deformation is considerably smaller for ARAMID and tensilized‐type PET than for PEN, although Standard PET shows the largest amount of creep. In addition, creep measurements under high humidity also show similar trends. Shrinkage measurements at 55°C for 100 h show that the shrinkage of ARAMID is lower than that of PET and PEN. The relationship between the polymeric structure and dimensional stability are also discussed. Based on the creep and shrinkage behavior, ARAMID and tensilized‐type PET seem to be suitable for advanced magnetic tapes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1477–1498, 2002; DOI 10.1002/app.10012     

Correlations between creep,shrinkage, and dynamic mechanical characteristics of magnetic tape materials

Creep compliance, shrinkage, and dynamic mechanical analysis (DMA) results are presented and discussed for developmental magnetic tapes made from PEN and metalized PET (Spaltan®) substrates as well as PEN substrate samples cut from wide‐stock in the machine and transverse directions. Curve fit parameters from the Kelvin‐Voigt model are discussed to shed light on the creep‐compliance characteristics, particularly the roll‐off characteristics observed at elevated temperatures and long time periods. Characteristic peaks observed in storage and loss moduli measured using DMA that correspond with molecular movement provide information that assists with the understanding of creep‐compliance and shrinkage behavior for these materials. Such movement corresponds with dimensional instabilities that need to be understood for future generations of advanced digital magnetic tapes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Long‐term mechanical and viscoelastic behavior of constitutive polymeric materials used for magnetic tapes

Creep‐compliance behavior of specially prepared magnetic tape materials was measured at elevated temperature levels to facilitate the use of a time–temperature superposition (TTS) process. This TTS process allowed for the construction of master curves at a reference temperature of 30°C, which were used to predict the long‐term viscoelastic behavior of the magnetic particle (MP) and metal‐evaporated (ME) tapes used in the study. The specially prepared samples allowed for the use of a rule of mixtures technique to determine the long‐term creep compliance of the front coat and back coat used for the magnetic tapes. To test the validity of this procedure, the front coat, substrate, and back coat data determined through separate experiments were used to calculate creep compliances of simulated tapes. These calculated creep‐compliance curves were then compared to measured data for the actual magnetic tapes. After determination and validation of the front coat, substrate, and back coat creep‐compliance data sets, they were used to determine strain distributions when the tapes are stored in a reel. Strain distributions were calculated for two cases, which reflect how tapes are stored in different drives: (1) the front coat (magnetic + nonmagnetic layer) is oriented away from the hub, and (2) the front coat is oriented toward the hub. Results showed that strain in the critical front coat of a tape is lower if it is stored with the front coat oriented toward the hub. In addition, the use of the creep‐compliance data showed that the MP tape front coat is more susceptible to creep than the ME tape front coat. The strain distributions in future magnetic tapes were also simulated by reducing the thickness and compliance of the layers. Results showed the importance of using lower compliance front coat, substrate, and back coat materials if thinner tapes are to be developed to increase the volume of information that can be stored in a magnetic tape reel. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1142–1160, 2001     

Thermally stimulated creep (TSCr) study of viscoelastic behavior and physical aging of a polymeric matrix composite for spacecraft structures

Thermally Stimulated Creep (TSCr) mechanical spectroscopy has been used to analyze molecular movements in KMU‐4lcarbon/epoxy composite material around the glass transition temperature. This technique is powerful to characterize the microstructure and micromechanical properties of the epoxy matrix and their evolution upon thermal aging. Three cooperative submodes have been distinguished by resolving the fine structure of the material complex α‐retardation mode. The elementary processes constituting this mode possess activation enthalpies and preexponential factors that strongly depend on the thermal history of the sample. The activation parameters of the composite are subject to perceptible evolution due to postcuring degradation. The α‐mode associated complex spectrum shifts towards higher temperatures by 27°C as a consequence of a series of quenching in the temperature range 260 to 0°C; the material shows a rise in the fragility and a deterioration in the crack‐growth resistance qualities. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 342–350, 2002     

Viscoelastic analysis applied to the determination of long‐term creep behavior for magnetic tape materials

Creep‐compliance experiments were performed for three representative magnetic tapes. Two of these tapes used a magnetic particle (MP) coating, and one used a metal‐evaporated (ME) coating. The MP tapes used the following polyester substrates: semitensilized poly(ethylene naphthalate) (PEN) and supertensilized poly(ethylene terephthalate). The ME tape used an aromatic poly(amide) or aramid substrate. Time–temperature superposition was used to make creep‐compliance predictions at 30 and 50°C reference temperatures. Comparisons were made with dimensional stability requirements based on position error signal (PES) specifications for magnetic tape drives along with in‐cartridge creep specifications based on PES measurements. Circumferential and lateral creep strains were determined that account for storage of the tapes in a reel, and creep strains were predicted for future tapes with thinner, lower compliance coatings. A rule of mixtures method was also used to extract compliance information for individual layers of MP‐PEN tapes, and stress profiles through the thickness of the tapes were determined. Additional measurements and analyses were performed to determine the creep recovery and shrinkage characteristics for the magnetic tapes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1106–1128, 2006     

Viscoelastic characteristics of magnetic tapes with PEN substrates

Viscoelastic characteristics of magnetic tapes with poly(ethylene naphthalate) substrates were studied using experimental techniques. Measurements were made using samples cut from commercially available tapes, and solvents were used to remove front and/or back coat layers to obtain substrates and dual‐layer samples. Experimental results allowed for fundamental compliance and viscosity parameters to be determined using a Kelvin‐Voigt model. Rates of creep‐compliance were also predicted, and comparisons were made with results for tapes that used poly(ethylene terephthalate) and aromatic poly(amide) substrates. Dynamic mechanical analysis (DMA) was used to help make correlations between viscous characteristics measured from the creep‐compliance results and molecular characteristics of the substrates. Time‐temperature superposition (TTS) was used to predict creep‐compliance over extended time periods, and a rule‐of‐mixtures method was used to predict the compliance of constitutive layers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical,hygroscopic, and thermal properties of ultrathin polymeric substrates for magnetic tapes

Mechanical, hygroscopic, and thermal properties of improved ultrathin polymeric films for magnetic tapes are presented. These films include poly(ethylene terephthalate) (PET), poly(ethylene naphthalate) (PEN), and aromatic polyamide (ARAMID). PET films are currently the most commonly used polymeric substrate material for magnetic tapes, followed by PEN and ARAMID. The thickness of the films ranges from 6.2 to 4.8 μm. Tensile tests were run to obtain the Young's modulus, F5 value, strain at yield, breaking strength, and strain at break. The storage modulus, E′, and the loss tangent, tan δ, were measured using a dynamic mechanical analyzer (DMA) at temperature ranges of ?50 to 150°C (for PET) and ?50 to 210°C (for PEN and ARAMID) and at a frequency range of 0.016–28 Hz. Frequency–temperature superposition was used to predict the dynamic mechanical behavior of the films over a 28‐decade frequency range. Short‐term longitudinal creep behavior of the films during 10, 30, 60, and 300 s, 7 MPa, were measured at 25 and 55°C. Long‐term longitudinal creep measurements were performed at 25, 40, and 55°C for 100 h. The Poisson's ratio and 50‐h long‐term lateral creep were measured at 25°C/15% RH, 25°C/50% RH, 25°C/80% RH, and 40°C/50% RH. The in‐plane coefficient of hygroscopic expansion (CHE) at 25°C/20–80% RH and the coefficient of thermal expansion (CTE) at 30–70°C were measured for all the samples. The properties for all films are summarized. The relationship between the polymeric structure and the mechanical and physical properties are discussed, based on the molecular structure, crystallinity, and molecular orientation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3052–3080, 2003     

Modeling for prediction of restrained shrinkage effect in concrete repair

A general model of autogenous shrinkage caused by chemical reaction (chemical shrinkage) is developed by means of Arrhenius' law and a degree of chemical reaction. Models of tensile creep and relaxation modulus are built based on a viscoelastic, three-element model. Tests of free shrinkage and tensile creep were carried out to determine some coefficients in the models. Two-dimensional FEM analysis based on the models and other constitutions can predict the development of tensile strength and cracking. Three groups of patch-repaired beams were designed for analysis and testing. The prediction from the analysis shows agreement with the test results. The cracking mechanism after repair is discussed.     

Viscoelastic and shrinkage behavior of ultrathin polymeric films

Viscoelastic and shrinkage characteristics of five ultrathin polymeric films are presented. These films include poly(ethylene terephthalate) or PET, poly(ethylene naphthalate) or PEN, an aromatic polyamide (ARAMID), a polyimide (PI), and poly(benzoxazole) or PBO. PET film is currently the standard substrate used for magnetic tapes, and the other four films represent alternative substrates with improved material properties. Thicknesses of the films range from 14.4 μm for PET to 4.4 μm for ARAMID. A creep apparatus is used to measure the viscoelastic and shrinkage characteristics of the films. The largest amount of creep compliance was measured for PET followed by PI, PEN, ARAMID, and PBO. Creep velocity was highest for PET and PI, followed by ARAMID, PEN, and PI. Shrinkage measurements at 50°C for 100 h show that PEN shrinks more than all the other substrates. Time–temperature superposition is used to predict long-term creep behavior, and relationships between polymeric structure and viscoelastic behavior are also discussed. Based on their relative cost and creep behavior, PEN and ARAMID substrates appear to be suitable alternatives to PET. © 1995 John Wiley & Sons, Inc.     

Evaluation of a basic creep model with respect to autogenous shrinkage

This paper shows the results obtained from an experimental study to evaluate a basic creep model. In this study, four different mixture proportions were placed, and tests on the specimens for autogenous shrinkage and basic creep were conducted with respect to age and stress level. The primary test variable was the water/cement ratio (w/c).From this research, it was found that for low w/c concrete, as well as at an early age of normal-strength concrete, a significant difference exists between apparent basic creep (including autogenous shrinkage) and real basic creep (excluding autogenous shrinkage). Furthermore, creep strain was not directly proportional to the applied stress level after one day. It was also discovered that when the current basic creep model that includes autogenous shrinkage is used in creep analysis, considerable errors as well as some computational problems may result. We therefore recommend modifying the equations of the current basic creep model with respect to autogenous shrinkage.     

Electrical behavior of PET films coated with nanostructured organic–inorganic hybrids

Hybrid coatings, based on poly(ethylene oxide) (PEO) or polycaprolactone (PCL) and silica (SiO₂), at different organic–inorganic compositions have been used to coat PET films employed in the electric industry to produce capacitors. The overall electrical behavior of the coated films has been investigated. The electrical strength of the coated films increases up to 10–15% of the uncoated ones regardless of polymer type (PEO/PCL) and amount of inorganic phase, as far as the thickness of the coating is below 5 μm. A systematic increase of surface electrical conductivity is found in all coated samples which however still behave as insulators. Permittivity and loss factor also increase particularly at low frequencies (< 10 Hz) on account of the presence of ions deriving from the sol–gel process and on the presence of interfacial polarization probably related to the coatings nanostructurated morphology which leads to phase separation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4870–4877, 2006     

Nanoindentation behavior of ultrathin polymeric films

Measurement of the mechanical properties of nanoscale polymeric films is important for the fabrication and design of nanoscale layered materials. Nanoindentation was used to study the viscoelastic deformation of low modulus, ultrathin polymeric films with thicknesses of 47, 125 and 3000 nm on a high modulus substrate. The nominal reduced contact modulus increases with the indentation load and penetration depth due to the effect of substrate, which is quantitatively in agreement with an elastic contact model. The flow of the nanoscale films subjected to constant indentation loads is shear-thinning and can be described by a linear relation between the indentation depth and time with the stress exponent of 1/2.     

Dynamic mechanical analysis of magnetic tapes at ultra‐low frequencies

A custom, ultra‐low frequency, dynamic mechanical analyzer (ULDMA) has been developed to study the correlated effects of temperature and frequency on the viscoelastic behavior of magnetic tapes. It has been used to acquire data needed for the development of future magnetic tapes that require an archival life of up to 100 years. A range of elevated temperatures is used to simulate real‐world storage environments, which enables the investigation of how the viscoelastic characteristics of tape samples influence the extent to which the tape deforms. The experiments and subsequent analysis examine the influence of the molecular structure on the viscoelasticity of magnetic tapes. Experiments were performed on a variety of magnetic tapes, including poly(ethylene terephthalate) (PET), poly(ethylene naphthalate) (PEN), metalized PET (M‐PET), and metalized Spaltan (M‐SPA). Additional experiments examined PEN and PET substrates by removing the front and back magnetic layers from the tape sample. Because of the viscoelastic behavior of the tapes, a time delay was present between the strain and stress signals, which was determined using a Fourier transform program. The elastic modulus (E), storage modulus (E′), loss modulus (E″), and loss tangent (tan δ) were obtained from the time delay for each of the ULDMA experiments at 25, 50, and 70°C over the frequency range of 0.0100–0.0667 Hz. Plots of these mechanical characteristics demonstrate the ability of frequency and temperature to affect trends associated with mechanical and thermal properties. Finally, some samples displayed an initial relaxation during the ULDMA experiments, which, when modeled using Maxwell's viscoelastic model, provided an insight into the relaxation characteristics of the samples. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Co‐extruded polymeric films for gas separation membranes

In recent years, gas separation has become an important step in many production process streams and part of final products. Through the use of melt co‐extrusion and subsequent orientation methods, gas separation membranes were produced entirely without the use of solvents, upon which current methods are highly dependent. Symmetric three layer membranes were produced using poly(ether‐block‐amide) (PEBA) copolymers, which serve as a selective material that exhibits a high CO₂ permeability relative to O₂. Thin layers of PEBA are supported by a polypropylene (PP) layer that is made porous through the use of two methods: (1) inorganic fillers or (2) crystal phase transformation. Two membrane systems, PEBA/(PP + CaCO₃) and PEBA/β‐PP, maintained a high CO₂/O₂ selectivity while exhibiting reduced permeability. Incorporation of an annealing step either before or after orientation improves the membrane gas flux by 50 to 100%. The improvement in gas flux was a result of either elimination of strain induced crystallinity, which increases the selective layer permeability, or improvement of the PP crystal structure, which may increase pore size in the porous support layer. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39765.     

Dielectric behavior of sulfonated poly(styrene–isobutylene–styrene) triblock copolymer thin films

Sulfonated, block copolymers have traditionally been studied for applications in fuel cells and chemical protective clothing, among others. As such, most investigations have focused on the evaluation of transport properties and the selectivity and permeability of the polymer membranes. This work, however, focuses on the electrical characterization of sulfonated poly(styrene–isobutylene–styrene) (SIBS) triblock copolymer thin films. More specifically, the dielectric properties of SIBS are evaluated as a function of critical parameters such as frequency, sulfonation percent, and the polymer concentration. The results show that the dielectric constant increases with sulfonation percent and polymer concentration to values as high as 13,600. This work also provides insights into the correlation of SIBS electrical properties with its chemical structure and morphology. The structure–property relationship is derived through a combination of techniques including: elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and atomic force microscopy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45662.     

Analytical approach of creep behavior of carpet yarn

Based on mechanical models, the creep behavior of carpet yarns after dynamic loading was investigated. For prediction the creep elongation, the frequently used mechanical models reported in the literature were analyzed. The mechanical models which were used in this article were: standard linear model, four‐element model, two‐component Kelvin's model, and Eyring's model. The obtained creep formulas were fitted to experimental creep data, and the parameters of the model can be obtained using the Marquardt algorithm for nonlinear regression. When comparing the experimental creep curve with the fitted curve from the mechanical model, it is clear that the four‐element model explain the experimental creep curve better. During tufting machine stops, the carpet yarns were undergone constant load. The confirmed viscoelastic model will be used to calculate total creep elongation during carpet machine stoppage. Thus, the start‐up marks which occurred at carpet machine restarts can be exactly eliminated by adjusting the feeding length according to the creep elongation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

一个胶凝原油的蠕变模型

为了研究胶凝原油的启动屈服过程,确定胶凝原油的蠕变模型至关重要。基于不同剪应力下胶凝原油的蠕变特性,建立了具有黏性流的黏弹性固体流变模型来描述胶凝原油的黏弹流变特性,通过试验验证该模型能精确描述胶凝原油的黏弹性蠕变过程;若施加的剪应力高于胶凝原油的塑性屈服应力,胶凝原油的蠕变将从稳定流变阶段很快达到加速流变阶段,表现为典型的黏弹塑性特征,将非线性黏塑性体和具有黏性流的黏弹性固体流变模型串联起来得到一个非线性黏弹塑性剪切流变模型,该模型能充分反映胶凝原油的加速剪切蠕变过程,并与试验结果吻合的较好。     

Tensile creep behavior of SiCf/SiC ceramic matrix minicomposites

Single fiber-tow minicomposites represent the major load-bearing element of woven and laminate ceramic matrix composites (CMCs). To understand the effects of fiber type, fiber content, and matrix cracking on tensile creep in SiC_f/SiC CMCs, single-tow SiC_f/SiC minicomposites with different fiber types and contents were investigated. The minicomposites studied contained either Hi-Nicalon™ or Hi-Nicalon™ Type S SiC fibers with a boron nitride (BN) interphase and a chemical-vapor-infiltrated-silicon-carbide (CVI-SiC) matrix. Tensile creep was performed at 1200 °C in air. A bottom-up creep modeling approach was applied where creep parameters of the fibers and matrix were obtained separately at 1200 °C. Next, a theoretical model based on the rule of mixtures was derived to model the fiber and matrix creep-time-dependent stress redistribution. Fiber and matrix creep parameters, load transfer model results, and numerical modeling were used to construct a creep strain model to predict creep damage evolution of minicomposites with different fiber types and contents.     

Molded geometry and viscoelastic behavior of film insert molded parts

Virgin injection‐molded tensile specimens without any inserted film and four kinds of film insert molded (FIM) tensile specimens were prepared. They were annealed at 80°C to investigate the effect of residual stresses and thermal shrinkage of the inserted film on thermal deformation of tensile specimens. The FIM specimens with the unannealed film were bent after ejection in such a way that the film side was protruded and the warpage was reversed gradually during annealing and the film side was intruded. Warpage of the FIM specimen with the film annealed at 80°C for 20 days was not reversed during annealing. Processing of the FIM specimens have been modeled numerically to predict thermoviscoelastic deformation of the part and to understand the warpage reversal phenomenon (WRP). Nonisothermal three‐dimensional flow analysis was carried out for filling, packing, and cooling stages. The flow analysis results were transported to a finite element stress analysis program for prediction of deformation of the FIM part. The WRP was caused by the combined effect of thermal shrinkage of the inserted film and relaxation of residual stresses in the FIM specimen during annealing. It is expected that this study will contribute towards the improvement of the FIM product quality and prevention of large viscoelastic deformation of the molded part. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A modified quasi‐creep model for assessment of deformation of topas COC substrates in the thermal bonding of microfluidic devices: Experiments and modeling

The effects of thermomechanical properties of dissimilar polymer plates on thermal bonding were investigated and the resultant deformation of cover Topas COC plate was modeled using a simplified quasi‐creep model. The appropriate conditions for thermal bonding for minimal deformation of both the Topas cover and substrate plates could be established through simulation using the quasi‐creep model. Both the cover plate and the substrate containing microchannels were fabricated by injection molding. The elastic modulus of the COC plate at different temperatures was measured using three‐point bending test. The thermal bonding was conducted at different temperatures, pressures, and holding times. The deformation of the cover plate (consisting of Topas with a lower glass transition temperature, T_g) into the microchannel of the substrate plate (consisting of Topas with a higher T_g) was found to be significant even at lower bonding pressures when the bonding temperature was higher than a critical temperature. Such deformation was dependent on the viscoelastic creep behavior of the material and the thermal bonding temperature and load. This deformation behavior was predicted by the numerical model, and the predicted results agree well with the experimental data. The bonding strength of the sealed microchannels was evaluated using the burst test. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011