Toughening of epoxy systems by brominated epoxy

Blends of brominated epoxy (BE) and conventional epoxy resins were studied following curing with aliphatic triethylenetetramine (TETA), etheric (polyether diamine‐ PEA4), and aromatic (3,3′‐diamino diphenyl sulfone [DDS]) hardeners. The addition of BE resulted in an increase in T_g in all tested blends. Blends with 50 wt% BE cured with TETA demonstrated an increase in flexural modulus and flexural strength, while preserving the elongation. Blends with 40 wt% BE cured with PEA4 and 50 wt% BE cured with DDS resulted in a significant enhanced tensile elongation. The shear strength of all cured systems decreased moderately with the addition of BE exhibiting a mixed mode failure. Analysis of the fracture morphology using electron microscopy supported the increase of toughness levels as a result of incorporating BE to conventional epoxy. A unique nodular and rough fracture morphology was obtained, which is related to a toughening mechanism caused by the addition of BE. It was concluded that blends of BE and conventional epoxy could be used as structural adhesives having high T_g, enhanced mechanical properties and increased toughness. POLYM. ENG. SCI., 59:206–215, 2019. © 2018 Society of Plastics Engineers     

Residual stress in particulate epoxy resin by X-ray diffraction

Residual stress in particulate epoxy resin was investigated by X-ray diffraction. Microdeformation of incorporated Al and α-SiO₂ crystal, which was induced by the residual stress, could be detected as a shift of X-ray diffraction peak. The residual stress at the interface between the adherend and the particulate epoxy resin was found to decrease with the increase of volume fraction of filler. It was shown that the difference in the thermal expansion coefficients between the adherend and the particulate epoxy resin is much more effective on residual stress than the increment of Young's modulus owing to the incorporation of filler. When epoxy resin was cured on the Al plate, incorporated particles were subjected to a tensile stress; while cured on polytetrafluoroethylene sheet, particles were subjected to a compressive stress. The incorporation of some inorganic particles is considered effective to reduce the residual stress.     

Curing stresses in an epoxy polymer

Curing stresses in sheets of an epoxy polymer cured at 80°C, 120°C, and 135°C have been determined using the layer removal procedure. Tensile stresses were found to be present in the interior and compressive stresses near to the surface in all samples. Very low stresses were found to be present in material cured at 80°C, with a maximum compressive stress level close to 0.5 MN/m² and a maximum tensile stress close to 0.25 MN/m². Higher stress magnitudes were obtained when using higher curing temperatures, with values of more than 1 MN/m² (compressive) and 0.6 MN/m² (tensile) recorded for specimens cured at 135°C.     

Residual stresses in high-temperature ceramic eutectics

This paper explores residual thermal stresses in directionally solidified ceramic eutectics, a class of materials that has much promise for high-temperature structural applications. Residual strain tensors of both phases in a eutectic composite are measured by single crystal X-ray diffraction techniques. In the analysis the material is treated as fully anisotropic and the strain tensors, subsequently converted to stress tensors, are measured. Results are presented for two oxide eutectics, NiO–cubic ZrO₂ and YAG–Al₂O₃, the former having a large thermal expansion mismatch between the two phases and the latter having similar thermal expansion properties. It is discovered that large residual stresses (of the order of 1 GPa) can be present at room temperature in as-processed eutectic materials unless the thermal expansion behaviors of the constituent materials are very similar. Ultimately these measurements not only elucidate the stress state but, when compared to theory, give information about the degree of interfacial constraint between the two phases.     

Residual stresses in injection-molded amorphous polymers

Nonisothermal flow of a polymer melt into a cold cavity and its rapid cooling give rise to the buildup of flow and thermal stresses in the molded article. In the present investigation the resultant residual stresses (RS) induced by these two sources were studied in two stages. First, the flow-induced stresses were relaxed by proper heat treatment followed by quenching, resulting in only thermal stresses. The experimentally determined RS profiles in polysulfone and amorphous polyamide showed a parabolic shape and were correlated with the initial and final quenching temperatures, the glass transition temperature, and Biot Number. In the second stage, the combined effect of thermal- and flow-induced stresses was studied using injection-molded specimens prepared under a wide speptrum of molding conditions including melt and mold temperatures and injection rate and pressure. Results here indicated that the basic thermal-induced parabolic RS profiles are altered by the flow-induced stresses resulting in complicated profiles including local maxima and unbalanced RS. Finally, the tensile mechanical properties obatained for plaques molded under the various injection-molding conditions were studied and correlated in part with the previously determined RS profiles. Results have shown that a property gradient exists as a function of distance from both the gate and surface of the molded plaque.     

Residual thermal stresses in injection molded products

Nonisothermal flow of a polymer melt in a cold mold cavity introduces stresses that are partly frozen-in during solidification. Flow-induced stresses cause anisotropy of mechanical, thermal, and optical properties, while the residual thermal stresses induce warpage and stress-cracking. In this study, the influence of the holding stage on the residual thermal stress distribution is investigated. Calculations with a linear viscoelastic constitutive law are compared with experimental results obtained with the layer removal method for specimens of polystyrene (PS) and acrylonitrile butadiene-styrene (ABS). In contrast to slabs cooled at ambient pressures, which show the well-known tensile stresses in the core and compressive stresses at the surfaces, during the holding stage in injection molding, when extra molten polymer is added to the mold to compensate for the shrinkage, tensile stresses may develop at the surface, induced by the pressure during solidification.     

Residual stresses in injection molded polycarbonate rectangular bars

This study deals with the quantification of the residual stress profiles of injection molded rectangular bars with polycarbonate of various molecular weights. Determinations via the layer removal technique indicated that these bars can possess compressive stress of up to 10 MPa at the surface and up to 9 MPa in tension in the interior. The residual stress profile showed a shape similar to that observed in thermal quenching experiments, i.e., parabolic, for locations far away from the gate of the cavity. At locations near the gate of the cavity and for injection molding at high speed, the residual stress profile changed sign, going from compressive to tension at the surface and vice versa in the interior. These residual stress profiles were very dependent on gating geometry and location.     

Residual stresses in chemical vapour deposited diamond films

In this paper we report the determination of residual stresses in diamond films grown on Si(100) using a plate bending theory and a bi-metal theory combined with micro-Raman spectroscopy. Raman spectra show that with an increase in the film thickness, the characteristic diamond line shifts from higher wave numbers (>1332 cm⁻¹) to lower (<1332 cm⁻¹), indicating a change of compressive to tensile bi-axial stress with increase in the film thickness. A plate bending theory and a bi-metal theory are used to determine the distribution of the stress induced by the thermal mismatch. The modelled results show that the bi-axial stress decreases linearly along the film growth direction and the stress at the film/substrate interface decreases when the film becomes thicker. The difference from the Raman results is attributed to intrinsic stress.     

Residual stresses in polymeric passivation and encapsulation materials

The residual stresses caused by polyiinide (Pi 5878 and PI 2566), and silieone (3-6550 and 1-2577) films used as passivation/encapsulation layers in microelectronic circuit manufacturing are investigated by X-ray curvature measurements. For both PI types, the maximum stress is between 20–40 MPa. This stress is independent of film thickness for films thinner than 10 μm. For films thicker than this value, however, some dependency of the film stress on film thickness is observed. The variation of stress during the cure cycle is significantly different for PI 5878 and PI 2566. This is due to void nucleation and growth in the 5878 films during solvent volatilization. The silieone films have no residual stress at room temperature for all thicknesses. The compensating stresses in the Si wafer are insignificant for all cases studied.     

Residual stresses and aging in injection molded polypropylene

The residual stresses in injection molded bars of polypropylene have been examined using a stress relaxation method and by the layer removal technique. A positive value for the internal stress parameter was obtained with newly molded specimens and was found to be retained by specimens stored at liquid nitrogen temperature. The stress relaxation parameter reduced to zero both for specimens aged at room temperature and also for those aged at ?40°C. Nevertheless the relaxation behavior of specimens aged at all three temperatures was quite distinct. The layer removal technique showed that the stresses near to the surface were compressive and those in the interior tensile, in apparent contradiction to the interpretation of Kubat and Rigdahl for the meaning of a positive internal stress parameter. A marked reduction in stress levels on aging at room temperature was confirmed, however. The relevance of the relaxation spectrum of polypropylene to these observations is discussed.     

Residual stresses in marine coatings under simulated service conditions

Studies have been made of the effect of cyclic temperature changes and wet/dry cycling on the residual stresses in marine coatings applied to steel substrates. A thermoplastic and a thermoset have been use as single coatings and as bi-layers consisting of the thermoset applied on top of the thermoplastic. Cyclic changes associated with differential thermal expansion/contraction between substrate and coating and with water absorption or desorption were observed, and it was found in addition that progressive changes in residual stress were sometimes superimposed on the cyclic changes. The effect was larger with the thermoplastic coating than with the thermoset. The stresses developed in the bi-layers were generally smaller than those in single layer coatings and were generally less sensitive to the cyclic changes in conditions. The effects were partly controlled by the thicknesses of the two layers in the bi-layer coatings. Stresses as high as 6 MPa were measured during the course of this work, a significant fraction of the failure strength of the coatings.     

Residual stresses and birefringences in large,quenched samples

As large polymer samples are quenched rapidly, residual stresses (and birefringence) are frozen into the final part due to the different thermal/contraction histories of the surface and center portions. The present work on polystyrene, a continuation of earlier studies, deals with the effects of sample size and initial temperature; these results are treated with the genral theory of Lee, Rogers, and Woo. Finally, data for two other amorphous polymers, poly(methyl methacrylate) and polycarbonate, are presented; in these cases the simpler theory of Aggarwala and Saibel is used. The theories help explain the relative behavior of the three materials and are qualitatively useful. However, the compexity of the rheooptical response precludes doing a completely rigorous treatment.     

Moisture diffusion in epoxy systems

The moisture diffusion process of an epoxy system is studied as a function of epoxy‐amine stoichiometry and the resulting microstructure. Differences in diffusion behavior are related to the relative importance of diffusion through the low‐density and high‐density microstructural phases for different stoichiometries. Also, changes in saturation level with stoichiometry are explained by competing effects of free volume versus the content of the low‐density phase. Increasing the humidity level causes a corresponding increase in saturation level, while increasing the temperature causes more pronounced non‐Fickian behavior. The effects of absorbed moisture on the thermomechanical properties of the epoxies are also investigated. Reductions in the glass transition temperature, T_g, and moisture‐induced swelling strains are measured after exposure of samples to the three conditioning environments. Moisture‐induced swelling strains increase with increasing moisture content. The reductions in T_g range from 5 to 20°C and are generally larger for amine‐rich samples than for epoxy‐rich and stoichiometric samples. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 787–798, 1999     

谈微晶玻璃残余应力的测量方法

分析了微晶玻璃中残余应力的形成机理及表现特点,并对几种常用测定残余应力的方法进行了比较。提出 了用X射线衍射法和中子衍射方法组合运用并结合其他非破坏性测量方法来测定微晶玻璃残余应力。     

Residual thermal stresses in bismaleimide/carbon fiber composite laminates

This is a study of residual thermal stresses in composite laminates, due to curing cycles. An extended formulation of Classical Lamination Theory (CLT) is adopted, which is able to take into account geometrical nonlinear effects owed to finite displacements. The approach is applied to square asymmetric laminates that have different dimensions and thicknesses. Final laminate shapes are evaluated after complete curing cycles; they can be cylindrical or saddle-like, and their equilibrium configuration stable or unstable depending on thickness vs. side length ratio. The same laminates are stacked, press-cured and the radii of curvature experimentally measured. In addition, they are modeled by means of finite element method (FEM) codes, using both linear and nonlinear techniques. Except for the thick laminates, the results obtained using nonlinear theoretical and numerical approaches show good agreement with experiment. Thermal residual strains are computed from non-mechanical strains by subtracting laminae free thermal deformations; the corresponding stresses are evaluated through layer stiffnesses. Residual stresses are evaluated both theoretically and experimentally. For thicker laminates the disagreement is mainly due to a mixed viscous phenomenon which takes place in resin interlaminar layers and matrix intralaminae. The share of relaxed stresses is evaluated and methods that include optimal cooling path techniques are suggested.     

Residual stresses in polymers and their effect on mechanical behavior

Plates of bisphenol-A polycarbonate and poly(methyl methacrylate) have been quenched in ice water from temperatures slightly above their glass transition temperatures. Residual stresses are thus created, Measurement of these residual stresses has been accomplished by the “layer removal” method and the stress distributions through the thickness are presented. Compressive stresses, approximately 3000 psi, exist at the surface while tensile stresses-of at least 1000 psi exist in the interior. It is shown that these residual stresses can influence the notched Izod impact strengths for polycarbonates. The mechanism is thought to be suppression of craze initiation in advance of the notch due to the presence of residual compressive stresses for specimens notched prior to quenching. In the case of poly(methyl methacrylate), it is shown that compressive residual stresses at the surface can cause plastic yielding to occur in bending experiments resulting in permanent deformation and greater energy absorption.     

3-D molecular assembly of function in titania-based composite material systems

Various examples of composite titania-based nanostructured materials exhibiting cooperative functionalities between different active components are presented. The fabrication of these integrated composite materials is based on one-pot supramolecular templating techniques combined with acidic sol-gel chemistry. The defined 3-D nanoscale organization and integration of various functional components results in advanced optoelectronic and photonic applications such as visible light sensitization of mesoporous titania photocatalysts with cadmium sulfide nanocrystals acting as sensitizing integral part of the mesopore wall structure, narrow bandwidth emission from rare earth ion activated nanocrystalline mesoporous titania films, and mirrorless lasing in dye-doped hybrid organic/inorganic mesostructured titania waveguides.     

Characterization of epoxy thermosetting systems by differential scanning calorimetry

Differential Scanning Calorimetry (DSC) is used to study the curing behavior of epoxy systems. For non-catalyzed diamine-epoxy systems, the reaction enthalpy ΔH and the glass transition temperature T_g are evaluated and related to the structure of the hardener. A method is developed to determine the activation energy. The effect of variations in the amine-to-epoxy ratio r on T_g is also examined. A maximum value is observed for r = 1. Then, the influence of benzyldimethylamine as catalyst in an anhydride/DGEBA system and in three diamine/DGEBA systems is reported. In the cases of DDS and DDA curing agent the maximum value of T_g is shifted, to r = 0, 6. The results are explained by different reaction mechanisms.