Direct relationships between volume variations at macro and nanoscale in epoxy systems. PALS/PVT measurements

The free volume in epoxy systems fully cured with aminic hardeners having different chemical structures was studied by means of positron annihilation lifetimes spectroscopy. The results are compared with those obtained from the analysis of the macroscopic specific volume changes by using pressure-volume-temperature experimental technique. An excellent correlation between the volumes measured at macro and nanoscales was found. From this fact, it can be asserted that the variation of the specific volume is mainly controlled by the variation in the average size of sub-nanometer size local free volumes, which are fixed by the chemical structure of hardener in fully crosslinked epoxy networks. These results give the first evidence of the direct relation existing between macro and nanoscales in thermosetting networks.     

Tetraglycidyl epoxy resins and graphite fiber composites cured with flexibilized aromatic diamines

Studies were performed to synthesize new ether modified, flexibilized aromatic diamine hardeners for curing epoxy resins. The effect of moisture absorption on the glass transition temperatures of a tetraglycidyl epoxy, MY 720, cured with flexibilized hardeners and a conventional aromatic diamine was studied. Unidirectional composites, using epoxy-sized Celion 6000 graphite fiber as the reinforcement, were fabricated. The room temperature and 300°F mechanical properties of the composites, before and after moisture exposure, were determined. The Mode I interlaminar fracture toughness of the composites was characterized, using a double cantilever beam technique to calculate the critical strain energy release rate, G_IC.     

Properties and processing characteristics of dielectric-filled epoxy resins

A family of casting composites, epoxy resins with mineral fillers, having a range of electrical properties, are being developed. In such composites, the dielectric constant is controlled primarily by varying the filler material in composition and proportions. The present work reports on the mechanical properties of composites made with two types of filler, an alumina powder (XA3500 from ALCOA) and a BaTiO₃/TiO₂ ceramic powder (ATD-50 from Ampex). Dependence of mechanical properties on curing agents was also determined. Filler contents from 0 to 40 percent volume were used. Epoxy systems contained single epoxy resin with both amine and anhydride hardeners. Processing of the anhydride-cured systems was easier than that of the amine-based systems because of their lower viscosity and longer gel time of the former. However, the anhydride-cured systems required higher processing temperatures. Curing kinetics and molecular bonding were investigated using a combination of differential scanning calorimetry, dynamic mechanical thermal analysis, and scanning electron microscopy. Activation energies of 11.2 kcal/mole and 12.1 kcal/mole were obtained for the curing of the amine-based and the anhydride-based composites respectively, and a small difference in the glass transition temperature was also observed. These effects can be attributed to the difference in the structure of the curing agents. The epoxy resin cured with NMA is less ductile compared with those cured with MTHPA or MHHPA due to slight chemical modification on the ring structures. This dependence of ductility on curing agent was observed in specimens with different filler contents. Although the presence of the filler materials was found to enhance the mechanical properties of the epoxy, the fracture mode in these materials is still brittle.     

不同固化剂对环氧树脂玻璃化温度影响的分子动态模拟研究

提出了一个分子动态模拟方法研究环氧树脂玻璃化转变温度(Tg)随固化剂结构变化。首先,建立了固化环氧树脂的一些简单分子模型;然后是一个分子动态模拟(MD)被重复执行。用模拟得到的数据作V-T关系曲线,用曲线上的转折点确定Tg的值。该模拟值与计算值有很好的吻合,尽管与实验值有较大的偏差,固化剂对Tg的影响可以用MD模拟定性得到。所提出的方法对于开发具有提高固化效果的固化剂有潜在的意义。     

Viscoelastic characterization of high performance epoxy matrix composites

Dynamic mechanical analysis, stress relaxation, and creep experiments were performed to characterize the viscoelastic properties of a basic unmodified epoxy (Hercules 3501-6) and a modified multiphase epoxy (Hercules 8551-7), which are commonly used as matrices in high performance composites. The Arrhenius and WLF equations and a modified Standard Linear Solid (SLS) Model were used to quantify the viscoelastic behavior below, above, and at the glass transition temperatures, Tg. Both the modified and the unmodified epoxy systems exhibited a single relaxation peak above ambient temperature. The Tg of the modified epoxy at full cure was 170°C, which is 50°C lower than that of the basic epoxy. The glassy moduli of these two resin systems were found to be comparable, but the rubbery modulus of the modified epoxy was much lower than that of the basic epoxy system. However, the viscoelastic behavior of these two systems and their sensitivity to time-temperature may be considered to be quite similar if they are compared with respect to their corresponding glass transition temperatures.     

A comparative study on the preparation and characterization of aromatic and aliphatic bismaleimides‐modified polyurethane–epoxy interpenetrating polymer network matrices

Interpenetrating polymer networks of bismaleimide‐modified polyurethane–epoxy systems were prepared using the aliphatic and aromatic bismaleimides‐ and polyurethane‐modified epoxy and cured in the presence of 4,4′‐diaminodiphenylmethane. Infrared spectral analysis was used to confirm the polyurethane‐crosslinked epoxy (PU–EP). The matrices developed were characterized by mechanical, thermal, electrical, and morphological studies. The results obtained from the mechanical studies indicate that the incorporation of polyurethane and bismaleimides into epoxy increased the tensile strength, flexural strength, and impact strength, according to their nature and percentage concentration. The results obtained from the thermal and electrical studies indicate that the incorporation of polyurethane into epoxy decreased the thermal properties (glass transition temperature, heat distortion temperature (HDT), thermal stability) and electrical properties (dielectric strength, volume and surface resistivity, and arc resistance). The incorporation of aromatic bismaleimide into the polyurethane‐modified epoxy system increased the glass transition temperature, thermal stability, and electrical properties. Decreased values of glass transition and HDT were obtained in the case of aliphatic bismaleimide‐modified polyurethane–epoxy system. Surface morphology of modified epoxy systems was studied using scanning electron microscopy, and it was found that the polyurethane‐modified epoxy systems exhibited heterogeneous morphology and bismaleimides‐modified epoxy systems showed a homogeneous morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3592–3602, 2006     

Network structure and properties of imidazole-cured epoxy novolac adhesives

The structural characteristics of four epoxy adhesives, obtained by crosslinking an epoxy novolac with various levels of a substituted imidazole curing agent, were investigated and correlated with thermal and mechanical properties. Variations in network structure were characterized by measuring crosslink densities and by qualitatively assessing glassy state free volume from densities and coefficients of thermal expansion. Differential scanning calorimetry was used to obtain glass transition temperatures, and dynamic mechanical thermal analysis was used to follow primary (alpha) and secondary (beta) transitions. Bulk behavior was characterized by tensile modulus, strength, and toughness, together with compressive modulus and yield strength. The effect of sub-T_g aging on compressive yield strength was investigated as well. As the level of imidazole increased, crosslink density, and hence network packing efficiency and free volume, decreased. For fully cured networks, both the glass and the alpha transition temperatures increased with crosslink density. Calculated activation enthalpies and entropies indicated significant degrees of network cooperativity in the alpha transitions, particularly for the more highly crosslinked systems. Beta transition temperatures, however, were found to be independent of crosslink density. Bulk properties generally showed a dependence both on crosslink density and free volume. Yield stress, for example, was highest for the network with lowest crosslink density and free volume. Volume relaxation associated with physical aging also caused yield stress to increase.     

Preparation and characterization of chain‐extended bismaleimide modified polyurethane–epoxy matrices

Intercrosslinked networks of bismaleimide (BMI) modified polyurethane–epoxy systems were prepared from chain‐extended BMI and polyurethane modified epoxy and cured in the presence of 4,4′‐diaminodiphenylmethane. Infrared spectral analysis was used to confirm the grafting of polyurethane onto the epoxy skeleton. The prepared matrices were characterized by mechanical, thermal, and morphological studies. The results, obtained from the mechanical and thermal studies, reveal that the incorporation of polyurethane into epoxy increases the mechanical strength and decreases the glass‐transition temperature and thermal stability. The incorporation of chain‐extended BMI into polyurethane modified epoxy systems increases the thermal stability and both tensile and flexural properties, and decreases the impact strength and glass‐transition temperature. Surface morphologies of polyurethane modified epoxy and chain‐extended BMI modified polyurethane– epoxy systems were studied by scanning electron microscopy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1562–1568, 2003     

Curing of epoxidized linseed oil: Investigation of the curing reaction with different hardener types

The effect of the hardener type and amount on the curing reaction and the resulting thermal and mechanical performance characteristics of epoxidized linseed oil are studied in detail. The analysis of the curing mechanism reveals that due to steric hindrance, side reactions and/or fast gelation, the optimal mixing ratio of bio-based epoxy resins and hardeners has to be determined experimentally and cannot be calculated. The investigated thermosets exhibit a glass transition temperature of 12, 54, and 145°C after curing. The overall mechanical performance of the resulting resin ranges from soft and flexible to stiff and rigid, depending on the hardener type applied, which can be utilized in the formation of epoxy composites and coatings.     

Preparation and characterization of bismaleimide (N,N′‐bismaleimido‐4,4′‐diphenyl methane)–unsaturated polyester modified epoxy intercrosslinked matrices

An intercrosslinked network of unsaturated polyester–bismaleimide modified epoxy matrix systems was developed. Epoxy systems modified with 10, 20, and 30% (by weight) of unsaturated polyester were made by using epoxy resin and unsaturated polyester with benzoyl peroxide and diaminodiphenylmethane as curing agents. The reaction between unsaturated polyester and epoxy resin was confirmed by IR spectral studies. The unsaturated polyester toughened epoxy systems were further modified with 5, 10, and 15% (by weightt) of bismaleimide (BMI). The matrices, in the form of castings, were characterized for their mechanical properties. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) of the matrix samples were performed to determine the glass transition temperature (T_g) and thermal degradation temperature of the systems, respectively. Mechanical properties, viz: tensile strength, flexural strength, and plain strain fracture toughness of intercrosslinked epoxy systems, were studied by ASTM methods. Data obtained from mechanical and thermal studies indicated that the introduction of unsaturated polyester into epoxy resin improves toughness but with a reduction in glass transition, whereas the incorporation of bismaleimide into epoxy resin improved both mechanical strength and thermal behavior of epoxy resin. The introduction of bismaleimide into unsaturated polyester‐modified epoxy resin altered thermomechanical properties according to their percentage concentration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2853–2861, 2002     

Correlation between molecular structure,free volume,and physical properties of a wide range of main chain thermotropic liquid crystalline polymers

Physical phenomena such as glass transition temperatures, melting points, and relaxational behavior have been determined for a wide range of thermotropic liquid crystalline polymers (TLCPs) and polycarbonate (PC). Damping intensities of rigid TLCPs during glass transition are greater than those of semirigid and semiflexible TLCPs. Positron annihilation lifetime spectroscopy was also employed to evaluate free volume parameters of polymers. In general, the positron annihilation lifetime spectroscopy (PALS) free volume parameters show that all TLCPs have much smaller, fewer free volume sites compared with PC. Correlations were found between PALS free volume parameters and glass transition temperature, dynamic mechanical damping strength, and bulk density where greater free volume parameters corresponded to higher glass transition temperatures, greater damping strength, and lower density. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2252–2267, 2001     

Influence of cure conditions on out‐of‐autoclave bismaleimide composite laminates

Bismaleimides (BMI) are thermosetting polymers that are widely used in the aerospace industry due to their good physical properties at elevated temperatures and humid environments. BMI‐based composites are used as a replacement for conventional epoxy resins at higher service temperatures. Out‐of‐Autoclave (OOA) processing of BMI composites is similar to that of epoxies but requires higher cure temperatures. Polymer properties such as degree of cure and crosslink density are dependent on the cure cycle used. These properties affect mechanical strength as well as glass transition temperature of the composite. In the current research, carbon fiber/BMI composite laminates were manufactured by OOA processing. The void content was measured using acid digestion techniques. The influence of cure cycle variations on glass transition temperature and mechanical strength was investigated. Properties of manufactured specimens were compared with that of conventional autoclave cured BMI composites. Laminates fabricated via OOA processing exhibited properties comparable to that of autoclave cured composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43984.     

Experimental Investigation on the Damping Behaviors of Epoxies with Different Epoxy Value

In this article, five different epoxies including a new kind of flexible epoxy having low glass transition temperatures (11 ～ 28°C) were prepared using polyamine as curing agent. Damping mechanical tests show that compared with other common available epoxies, the flexible epoxy has high loss factor over broad frequency and temperature range. Activation energy corresponding to glass transition process of different epoxies has been calculated from the temperature corresponding to tan δ_max values, obtained at different measurement frequencies. The maximum value of loss factor is 0.71 and the Tg varies from 11 to 28°C, indicating the flexible epoxy can be used as damping polymer materials in common temperature or frequency range.     

Time-temperature–transformation (TTT) diagrams of high Tg epoxy systems: Competition between cure and thermal degradation

The cure behavior and thermal degradation of high T_g epoxy systems have been investigated by comparing their isothermal time-temperature-transformation (TTT) diagrams. The formulations were prepared from di- and trifunctional epoxy resins, and their mixtures, with stoichiometric amounts of a tetrafunctional aromatic diamine. The maximum glass transition temperatures (T_g∞) were 229°C and > 324°C for the fully cured di- and trifunctional epoxy materials, respectively. Increasing functionality of the reactants decreases the times to gelation and to vitrification, and increases the difference between T_g after prolonged isothermal cure and the temperature of cure. At high temperatures, there is competition between cure and thermal degradation. The latter was characterized by two main processes which involved devitrification (decrease of modulus and T_g) and revitrification (char formation). The experimentally inaccessible T_g∞ (352°C) for the trifunctional epoxy material was obtained by extrapolation from the values of T_g∞ of the less highly crosslinked systems using a relationship between the glass transition temperature, crosslink density, and chemical structure.     

Influence of Curing Agents Molecular Structures on Interfacial Characteristics of Graphene/Epoxy Nanocomposites: A Molecular Dynamics Framework

This paper presents a comprehensive molecular dynamics study on the effects of the stoichiometric ratio of epoxy:hardener, hardener's linear and cyclic structure, and number of aromatic rings on the interfacial characteristics of graphene/epoxy nanocomposite. The van der Waals gap and polymer peak density as a function of the type of the hardener is calculated by analyzing the local mass density profile. Additionally, steered molecular dynamics are used to conduct normal pull-out of graphene to study the effect of the mentioned features of hardeners on the interfacial mechanical properties of nanocomposites, including traction force, separation distance, and distribution quality of reacted epoxide rings in the epoxy. Influence of the hardeners on the damage mechanism and its initiation point are also studied by analyzing the evolution of local mass density profile during the normal pull-out simulation. It is seen that stoichiometric ratio and geometrical structure of the hardeners affect the interfacial strength. It is also revealed that the hardener type can change the epoxy damage initiation point. The damage occurs in the interphase region for a higher stoichiometric ratio or cyclic structure of hardener. In comparison, for hardener's lower stoichiometric ratio and non-cyclic structure, failure begins in the epoxy near graphene layers.     

端氨基树枝状大分子/环氧树脂体系固化动力学的FTIR研究

用傅立叶变换红外光谱(FTIR)法研究了双酚A二缩水甘油醚环氧树脂(GEBA)用低代端氨基聚(酯-胺)树枝状大分子G1.0(NH2)3、G1.5(NH2)8和聚(胺-酰胺)树枝状大分子PAMAM1.0(NH2)4作为固化剂的等温固化动力学,得到了不同温度下转化率与固化时间及反应速率与固化时间的关系.与小分子固化剂相比,端氨基树枝状大分子作固化剂时环氧基转化率在反应开始时增长得更快,较高代树枝状大分子在高温下固化环氧树脂时尤其如此.在相同温度和时间下,PAMAM1.0(NH2)4/DGEBA、G1.0(NH2)3/DGEBA、G1.5(NH2)8/DGEBA体系的转化率依次增大.进一步估算了3个体系在一定转化率下的固化反应表观活化能.在相同转化率时,用G1.5(NH2)8、PAMAM1.0(NH2)4、G1.0(NH2)3作固化剂的体系表观活化能依次减小.     

Optimierung cycloaliphatischer Epoxidharzsysteme mit Siliconkautschuk

The high crosslink density of epoxy resins with high glass transition temperature, high strength, etc., used in many high-performance applications, causes the undesired brittleness of these materials and, hence, internal stress. For the optimization of their properties, cycloaliphatic epoxy resins were modified with elastomeric silicone. Two different modifying concepts, i. e. dispersion and mixing, were characterized using mechanical testing, dynamic-mechanical analysis and scanning electron microscopic studies as well as measurement of the expansion coefficient and the shrinkage. The modification with silicone, in general, reduces the modulus and improves the fracture toughness of the resins. Due to the two-phase structure of the resins prepared by the dispersion method, the glass transition temperature of the epoxy matrix is practically not depressed, and the tendency to enhance stress is less marked compared to the mixing method.     

Toughening of trifunctional epoxy system. V. Structure–property relationships of neat resin

This work presents an investigation into the structure–property relationships of a cured highly crosslinked epoxy/amine resin system. The mechanical, physical, and thermal properties of the cured and postcured networks were measured and compared to the chemical structures. Crosslink density was shown to be dependent upon secondary amine conversion and it determined the glass transition temperatures, water uptake, density, toughness, and compressive strength. Other properties such as compressive modulus and yield stress were determined by more short‐range molecular motions. Curing at a temperature of 150°C was shown to be the minimum temperature required to “completely” cure the network and achieve optimum mechanical, physical, and thermal properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 237–248, 2000     

Thermal and mechanical properties of tetra‐functional mesogenic type epoxy resin cured with aromatic amine

A novel tetra‐functional epoxy monomer with mesogenic groups was synthesized and characterized by ¹H‐NMR and FTIR. The synthesized epoxy monomer was cured with aromatic amine to improve the thermal property of epoxy/amine cured system. The glass transition temperature (T_g) and coefficient of thermal expansion (CTE) of the cured system were investigated by dynamic mechanical analysis and thermal mechanical analysis. The properties of the cured system were compared with the conventional bisphenol‐A type epoxy and mesogenic type epoxy system. The storage modulus of the tetra‐functional mesogenic epoxy cured systems showed the value of 0.96 GPa at 250 °C, and T_g‐less behavior was clearly observed. The cured system also showed a low CTE at temperatures above 150 °C without incorporation of inorganic components. These phenomena were achieved by suppression of the thermal motion of network chains by introduction of both mesogenic groups and branched structure to increase the cross linking density. The temperature dependency of the tensile property and thermal conductivity of the cured system was also investigated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46181.     

Phosphonate‐containing bismaleimide resins. II. Preparation and characteristics of reactive blends of phosphonate‐containing bismaleimide and epoxy

Two kinds of phosphonate‐containing bismaleimide (BMI) monomers, phenyl‐(4,4′‐bismaleimidophenyl) phosphonate and ethyl‐(4,4′‐bismaleimido‐phenyl) phosphonate, were synthesized and added through blending to two epoxy systems for the study of their applications as reactive flame retardants. The thermal behaviors of the BMI monomers in both kinds of epoxy systems, bisphenol and phenol–novolac, were similar. An increase in the BMI contents increased the storage modulus and glass‐transition temperature but slightly reduced the mechanical strength of the epoxy blends. The pyrolysis models of both BMI blends in the two epoxy systems were quite alike. Although the initial pyrolysis temperatures of all the blending systems gradually decreased as the phosphorous content increased, the flame retardancy of all the phosphonate‐containing epoxy systems was promoted significantly by increasing contents of BMI. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2375–2386, 2004