Preparation and mechanical properties of modified epoxy resins with flexible diamines

Diglycidyl ether of bisphenol A (DGEBA) is one of the most widely used epoxy resins for many industrial applications, including cryogenic engineering. In this paper, diethyl toluene diamine (DETD) cured DGEBA epoxy resin has been modified by two flexible diamines (D-230 and D-400). The cryogenic mechanical behaviors of the modified epoxy resins are studied in terms of the tensile properties and Charpy impact strength at cryogenic temperature (77 K) and compared to their corresponding properties at room temperature (RT). The results show that the addition of flexible diamines generally improves the elongation at break and impact strength at both RT and 77 K. The exception is the impact strength at 77 K filled with 21 wt% and 49 wt% D-400. Further, two interesting observations are made: (a) the cryogenic tensile strength increases with increasing the flexible diamine content; and (b) the RT tensile strength can only be improved by adding a proper content of flexible diamines. It is concluded that the addition of a selected amount namely 21–78 wt% of D-230 can simultaneously strengthen and toughen DGEBA epoxy resins at both RT and 77 K. However, only the addition of 21 wt% D-400 can simultaneously enhance the strength and ductility/impact strength of DGEBA epoxy resins at RT. The impact fracture surfaces are examined using scanning electron microscopy (SEM) to explain the impact strength results. Finally, differential scanning calorimetry (DSC) analysis shows that the glass transition temperature (T_g) decreases with increasing the flexible diamine content. The presence of a single T_g reveals that the flexible diamine-modified epoxy resins have a homogeneous phase structure.     

Reinforcement of epoxy resins with multi-walled carbon nanotubes for enhancing cryogenic mechanical properties

Epoxy resins are widely applied in cryogenic engineering and their cryogenic mechanical properties as important parameters have to be improved to meet the high requirements by cryogenic engineering applications. Carbon nanotubes (CNTs) are regarded as exceptional reinforcements for polymers. However, poor carbon nanotube (CNT)–polymer interfacial bonding leads to the unexpected low reinforcing efficiency. This paper presents a study on the cryogenic mechanical properties of multi-walled carbon nanotube reinforced epoxy nanocomposites, which are prepared by adding multi-walled carbon nanotubes (MWCNTs) to diglycidyl ether of bisphenol-F epoxy via the ultrasonic technique. When the temperature decreases from room temperature to liquid nitrogen temperature (77 K), a strong CNT–epoxy interfacial bonding is observed due to the thermal contraction of epoxy matrix because of the big differences in thermal expansion coefficients of epoxy and MWCNTs, resulting in a higher reinforcing efficiency. Moreover, synthetic sequence leads to selective dispersion of MWCNTs in the brittle primary phase but not in the soft second phase in the two phase epoxy matrix. Consequently, the cryogenic tensile strength, Young's modulus, failure strain and impact strength at 77 K are all enhanced by the addition of MWCNTs at appropriate contents. The results suggest that CNTs are promising reinforcements for enhancing the cryogenic mechanical properties of epoxy resins that have potential applications in cryogenic engineering areas.     

Simultaneous improvements in the cryogenic tensile strength,ductility and impact strength of epoxy resins by a hyperbranched polymer

Improvements in mechanical properties at low temperatures are desirable for epoxy resins such as diglycidyl ether of bisphenol A (DGEBA) that are often used in cryogenic engineering applications. In this study, a hydroxyl functionalized hyperbranched polymer (H30) is employed to improve the mechanical properties of a DGEBA epoxy resin at liquid nitrogen temperature (77 K). The results show that the tensile strength, failure strain (ductility) and impact strength at 77 K are simultaneously improved by adding a proper content of H30. The maximum tensile strength at 77 K is increased by 17.7% from 98.2 MPa of pure epoxy resin to 115.6 MPa of modified epoxy system for the 10 wt% H30 content. The failure strain at 77 K increases consistently with the increase of H30 content. The maximum impact strength at 77 K is attained by introduction of 10 wt% H30 with an improvement of 26.3% over that of pure epoxy resin. For the purpose of comparison, the mechanical properties of modified epoxy resins at room temperature (RT) are also investigated. It is interesting to note that the impact strength is not lower at 77 K than that at RT for the modified systems. Moreover, the glass transition temperature (T_g) is not reduced by the addition of H30 in appropriate amounts.     

Epoxy-functionalized polysiloxane reinforced epoxy resin for cryogenic application

The poor cryogenic mechanical properties of epoxy resins restrict their extensive application in cryogenic engineering fields. In this study, a newly synthesized epoxy-functionalized polysiloxane (PSE) is used to improve the cryogenic mechanical properties of bisphenol-F epoxy resin. The Fourier transform infrared spectra and nuclear magnetic resonance confirm the formation of epoxy-functionalized –Si–O–Si– molecular chain. The surface free energy test results show that the PSE has a better compatibility with epoxy resin. The mechanical test results show that the cryogenic tensile strength, failure strain, fracture toughness, and impact strength of epoxy resin is improved significantly by adding the suitable amounts of PSE. Compared to the neat epoxy resin, the maximum tensile strength (196.92 MPa, an improvement of 11.2%), failure strain (2.97%, an improvement of 33.8%), fracture toughness (3.05 MPa·m^1/2, an improvement of 30.7%) and impact strength (40.55 kJ m⁻², an improvement of 14.8%) at cryogenic temperature (90 K) is obtained by incorporating 10 wt % PSE into the neat epoxy resin. Moreover, the results also indicated that the tensile strength, Young's modulus, and fracture toughness of epoxy resin with the same PSE content at 90 K are higher than that at room temperature (RT). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46930.     

Synthesis and cryogenic properties of polyimide-silica hybrid films by sol-gel process

Polyimide-silica hybrid films were prepared from tetraethoxysilane (TEOS) and polyamic acid (PAA) via sol-gel process in the solution of N,N-dimethylacetamide (DMAc). The cryogenic mechanical and electrical properties of polyimide-silica hybrid films were studied taking into account the effects of silica content. The results indicated that the cryogenic modulus increased with the increase of silica content while the tensile strength and failure strain had a maximum value at proper silica contents. Moreover, the tensile strength and modulus of the hybrid films at cryogenic temperature (77 K) were obviously higher than those at room temperature, while the failure strain of the hybrid films was much lower at cryogenic temperature (77 K) than that at room temperature. The mean electrical breakdown strength of the hybrid films was shown to range from 151 to 225 kV/mm at cryogenic temperature (77 K).     

Simultaneously enhanced cryogenic mechanical behaviors of cyanate ester/epoxy resins by poly(ethylene oxide)‐co‐poly(propylene oxide)‐co‐poly(ethylene oxide) (PEO‐PPO‐PEO) block copolymer and clay

Cryogenic mechanical properties are important parameters for thermosetting resins used in cryogenic engineering areas. The hybrid nanocomposites were prepared by modification of a cyanate ester/epoxy/poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide) (PEO‐PPO‐PEO) system with clay. It is demonstrated that the cryogenic tensile strength, Young's modulus, ductility (failure strain), and fracture resistance (impact strength) are simultaneously enhanced by the addition of PEO‐PPO‐PEO and clay. The results show that the tensile strength and Young's modulus at 77 K of the hybrid nanocomposite containing 5 wt% PEO‐PPO‐PEO and 3 wt% clay were enhanced by 31.0% and 14.6%, respectively. The ductility and impact resistance at both room temperature and 77K are all improved for the hybrid composites. The fracture surfaces of the neat BCE/EP and its nanocomposites were examined using scanning electron microscopy (SEM). Finally, the dependence of the coefficients of thermal expansion (CTE) on the clay and PEO‐PPO‐PEO contents was examined by thermal dilatometer. POLYM. COMPOS., 38:2237–2247, 2017. © 2015 Society of Plastics Engineers     

环氧树脂的超低温增韧研究

用一种新型含氮杂萘酮结构的聚醚腈酮(PPENK)及其与环氧聚醚的混合体系增韧环氧树脂,测试了增韧树脂体系在室温和液氮温度下的断裂韧性(Kic)和冲击强度。实验结果表明,加入一定量的PPENK及环氧聚醚后可大幅提高环氧树脂的超低温韧性。此外,还研究了PPENK对环氧树脂体系在室温和超低温下弯曲、压缩和拉伸性能的影响。     

Studies on characterization and cryogenic mechanical properties of polyimide-layered silicate nanocomposite films

Polyimide/layered silicate nanocomposites were prepared via in situ polymerization process from PMDA-ODA and organo-MMT in a solution of N,N-dimethylacetamide. XRD, FTIR, UV-vis analyses showed that at the content of 1 wt% MMT, MMT were well intercalated, exfoliated and dispersed in polyimide matrix. As the MMT content is more than 3 wt%, MMT agglomerates became severe as shown by the transparency and transmittance of the hybrid films. The cryogenic mechanical properties of the films at 77 K were studied and compared with those at room temperature. The cryogenic tensile strength showed the highest value at 1 wt% MMT content, and its strength, modulus and elongation at break were simultaneously increased than the pure PI film. The cryogenic elastic modulus exhibited an increasing trend until the MMT content reached 10 wt%. The cryogenic failure strain of hybrid films with 1-3 wt% MMT contents was greater than 10%, showing good ductility at 77 K. The tensile strength and modulus of the hybrid films at 77 K were generally higher than those at room temperature except at 20 wt% MMT for the strength.     

Durability of adhesives based on different epoxy/aliphatic amine networks

The mechanical and adhesives properties of epoxy formulations based on diglycidyl ether of bisphenol A cured with various aliphatic amines were evaluated in the glass state. Impact tests were used to determine the impact energy. The adhesive properties have been evaluated in terms single lap shear using steel adherends. Its durability in water at ambient temperature (24 °C) and at 80 °C has also been analyzed. The fracture mechanisms were determined by optical microscopy. It was observed a strong participation of the cohesive fracture mechanisms in all epoxy system studied. The 1-(2-aminoethyl)piperazine epoxy adhesive and piperidine epoxy adhesive presents the best adhesive strength and the largest impact energy. The durability in water causes less damage to piperidine epoxy networks. This behavior appears to be associated with the lower water uptake tendency of homopolymerised resins due to its lower hydroxyl group concentration.     

Surface functionalized carbon nanotubes and its effects on the mechanical properties of epoxy based composites at cryogenic temperature

Epoxies have a wide range of applications in fuel tank fabrication, aerospace, electrical, electronic, and automobile industries. However, these resins are quite brittle, showing poor mechanical performance, especially at cryogenic temperature. The properties of functionalized multi-walled carbon nanotube (MWCNTs)-reinforced epoxy composites were investigated to develop advanced composites for cryogenic use. Two methods were adopted to modify MWCNTs. MWCNTs were first treated by acid mixture, and then maleic anhydride (MA) and isophorone diisocyanate (IPDI) grafting was carried out. At last, the functionalized MWCNTs were integrated into epoxy to prepare MWCNT-reinforced epoxy composites. Raman and XPS analysis proved the effectiveness of acid mixture treatment and confirmed the grafting reaction of MA and IPDI with MWCNTs. TEM analysis indicated that MA and IPDI had been grafted onto the surface of MWCNTs and formed a thin layer. The tensile strength, Young’s modulus, and impact strength of composites at liquid nitrogen temperature (77 K) are all enhanced by the addition of MWCNTs. Results of dynamic mechanical analysis indicated that introducing a small amount of functionalized MWCNTs to epoxy can enhance their storage modulus at 77 K and glass-transition temperature of composites. The results indicated that surface modified MWCNTs can be effectively utilized to enhance the properties of epoxy-based composites at cryogenic temperature.     

Internal stress analysis of epoxy adhesively-boned joints based on their thermomechanical properties at cryogenic temperature

Internal stress analysis is essential to structural design of materials applied in cryogenic engineering. In this contribution, thermomechanical properties including dynamic thermomechanical properties and thermal expansion behavior of four epoxy resins, namely the polyurethane modified epoxy resin (PUE), diglycidyl ether of bisphenol A (DGEBA), tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol (TGPAP) were studied by dynamic thermomechanical analysis. Internal stress of the epoxy layer in the bonded joint was calculated based on the thermomechanical properties. Meanwhile, the structure-cryogenic property relationship of epoxy resins were investigated. Results demonstrate that internal stress in the four epoxies bonded joints is 6 ~ 21 MPa at −150°C, and is positively correlated with the average thermal expansion coefficient (CTE) of epoxy resins. TGDDM and TGPAP showed higher retention of lap shear strength both at −196°C and after temperature cycling due to their lower CTE. Morphology of the fractured surface of bonded joints demonstrated that internal stress is responsible for the severe interface failure at −196°C. It reveals that selection of epoxy resins with low CTE is beneficial for designing high-performance epoxy adhesive systems served at cryogenic temperature.     

Thermo-physical and impact properties of epoxy nanocomposites reinforced by single-wall carbon nanotubes

The thermo-physical properties and the impact strength of diglycidyl ether of bisphenol F (DGEBF) epoxy nanocomposites reinforced with fluorinated single-wall carbon nanotubes (FSWCNT) are reported. A sonication technique was used to disperse FSWCNT in the glassy epoxy network resulting in nanocomposites having large improvement in modulus with extremely small amount of FSWCNT. The glass transition temperature decreased approximately 30 °C with an addition of 0.2 wt% (0.14 vol%) FSWCNT, without adjusting the amount of the anhydride curing agent. This was because of non-stoichiometry of the epoxy matrix that was caused by the fluorine on the single-wall carbon nanotubes. The correct amount of the anhydride curing agent needed to achieve stoichiometry was experimentally examined by dynamic mechanical analysis (DMA). The storage modulus of the epoxy at room temperature (which is below the glass transition temperature of the nanocomposites) increased up to 0.63 GPa with the addition of only 0.30 wt% (0.21 vol%) of FSWCNT, representing an up to 20% improvement compared with the neat epoxy. The Izod impact strength slightly decreased when the amount of FSWCNT was increased to 0.3 wt%. The excellent improvement in the storage modulus was achieved without sacrificing impact strength.     

糠醇缩水甘油醚稀释的环氧体系的性能研究

通过力学性能和热性能测试研究了糠醇缩水甘油醚(FGE)稀释的双酚A环氧树脂(DGEBA)体系的固化性能和固化反应动力学。通过Málek自催化机理模型求得添加10%FGE的DGEBA与脂肪族聚酰胺固化剂的固化反应平均活化能为64.66kJ/mol,低于苄基缩水甘油醚(BGE)稀释体系。以FGE稀释的固化产物的拉伸强度达到62.93MPa,比BGE体系高出20%左右。拉伸伸长率达4.66%,是BGE体系的4倍左右。添加FGE的固化物冲击强度达36.17MPa,比BGE体系高出约70%左右。使用FGE和BGE的环氧固化物的玻璃化转变温度分别为46.32℃和52.36℃。FGE和BGE体系固化物的5%的热失重温度分别为260.79℃和194.59℃。FGE是1种良好的环氧树脂稀释剂。     

Preparation and Application of a New Curing Agent for Epoxy Resin

A new curing agent based on palmitoleic acid methyl ester modified amine (PAMEA) for epoxy resin was synthesized and characterized. Diglycidyl ether of bisphenol A (DGEBA) epoxy resins cured with different content of PAMEA along with diethylenetriamine (DETA) were prepared. The mechanical properties, dynamic mechanical properties, thermal properties, and morphology were investigated. The results indicated that the PAMEA curing agent can improve the impact strength of the cured epoxy resins considerably in comparison with the DETA curing agent, while the modulus and strength of the cured resin can also be improved slightly. When the PAMEA/epoxy resin weight ratio is 30/100, the comprehensive mechanical properties of the cured epoxy resin are optimal; at the same time, the crosslinking density and glass transition temperature of the cured epoxy resin are maximal.     

Preparation and characterization of poly(urea-formaldehyde) microcapsules filled with epoxy resins

The preparation of microcapsules applied to the fabrication of self-healing composites has been paid more attentions. A new series of microcapsules were prepared by in situ polymerization technology with poly(urea-formaldehyde) (PUF) as a shell material and a mixture of epoxy resins (diglycidyl ether of bisphenol A: DGEBPA) and 1-butyl glycidyl ether (BGE) as core materials. The microencapsulating process of core material was monitored using optical microscopy (OM). The chemical structure of microcapsule was characterized using Fourier-transform infrared spectroscopy (FTIR). Morphology and shell wall thickness of microcapsule were observed using metalloscope (MS), scanning electron microscopy (SEM) and OM, respectively. The effects of different pre-polymers, weight ratios of urea to formaldehyde (U-F) and the agitation rates on the physical properties of microcapsules were investigated. The storage stability of microcapsules at different times and temperatures was analyzed. The thermal properties of microcapsules were investigated using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results indicate that PUF microcapsules containing epoxy resins can be synthesized successfully, and during the microencapsulation, the epoxide rings in epoxy resins are hardly affected by the surrounding media. The rough outer surface of microcapsule is composed of agglomerated PUF nanoparticles. The size and surface morphology of microcapsule can be controlled by selecting different processing parameters. The microcapsules basically exhibit good storage stability at room temperature, and they are chemically stable before the heating temperature is up to approximately 238 °C.     

Effect of reactive poly(ethylene glycol) flexible chains on curing kinetics and impact properties of bisphenol‐a glycidyl ether epoxy

Bisphenol‐A glycidyl ether epoxy resin was modified using reactive poly(ethylene glycol) (PEO). Dynamic mechanical analysis showed that introducing PEO chains into the structure of the epoxy resin increased the mobility of the molecular segments of the epoxy network. Impact strength was improved with the addition of PEO at both room (RT) and cryogenic (CT, 77 K) temperature. The curing kinetics of the modified epoxy resin with polyoxypropylene diamines was examined by differential scanning calorimetry (DSC). Curing kinetic parameters were determined from nonisothermal DSC curves. Kinetic analysis suggested that the two‐parameter autocatalytic model suitably describes the kinetics of the curing reaction. Increasing the reactive PEO content decreased the heat flow of curing with little effect on activation energy (E_a), pre‐exponential factor (A), or reaction order (m and n). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

New epoxy resins based on recycled poly(ethylene terephthalate) as organic coatings

Glycolysis of poly(ethylene terephthalate), PET, waste using trimethylol propane (TMP), triethanolamine (TEA), diethylene glycol (DEG) and diethanolamine (DEA) was used to produce suitable hydroxy-oligomers for epoxy. The glycolyzed products were reacted with epichlorohydrine to prepare a series of di- and tetraglycidyl epoxy resins with different molecular weights. The glycolysis was carried out in presence of manganese acetate as a catalyst at normal and high pressure in presence and absence of xylene at 210 °C. The produced resins were cured with different mole ratios of 1-(2-amino ethyl) piprazine as curing agent at room temperature. The mechanical properties of the cured epoxy resins were evaluated. The chemical resistances of the cured resins were evaluated through salt spray resistance, hot water, solvents, acid and alkali resistance measurements. The data indicate that the cured epoxy resins based on glycolyzed oligomer of PET and DEA have excellent chemical resistances as organic coatings among other cured resins.     

Maleimido-functionalized spirobislactone having enhanced volumetric expansion on polymerization

An approach to enhancing the volumetric expansion on polymerization of spirobislactone is proposed. This approach suggests a molecular modification of spirobislactone through attaching a rigid pendant segment bearing maleimido group to its aromatic ring. An additional volumetric expansion is achieved from loose molecular packing in cured resins due to the steric hindrance effect among rigid pendent segments. Thus a new monomer, maleimido-functionalized spirobislactone (MFS), is prepared. In order to evaluate the volumetric expansion of MFS during curing, tetraglycidyl 4,4′-diamino diphenyl methane (TGDDM) is employed to cure with MFS. The volumetric expansion of MFS on curing is measured to be 12.3%, higher than that of net spirobislactone monomer. The existence of loose molecular packing in MFS/epoxy cured resins is demonstrated by morphology observation of the cured resin stained by the phosphotungstic acid (PTA), and the stained regions are observed to be nanoparticles. Such a cured resin, prepared from 20 mol% of MFS and 80 mol% of TGDDM epoxy resin, shows excellent toughness (Charpy impact strength 13,000 J/m²) and good mechanical strength (flexural strength 120 MPa, storage flexural modulus 4.2 GPa). Its glass transition temperature by dynamic mechanical thermal analysis (DMA) attains 227 °C, much higher than that of the cured resin from net spirobislactone and epoxy resin.     

Toughening of epoxy resins by hydroxy‐terminated,silicon‐modified polyurethane oligomers

Epoxy resins are among the most versatile engineering structural materials. A wide variety of epoxy resins are commercially available, but most are brittle. Several approaches have been used to improve the toughness of epoxy resins, including the addition of fillers, rubber particles, thermoplastics, and their hybrids, as well as interpenetrating polymer networks (IPNs) of acrylic, polyurethane, and flexibilizers such as polyols. This last approach has not received much attention; none of them have been able to suitably increase resin toughness with out sacrificing tensile properties. Therefore, in an attempt to fill this gap, we experimented with newly synthesized hydroxy‐terminated silicon‐modified polyurethane (SiMPU) oligomers as toughening agents for epoxy resins. SiMPU oligomers were synthesized from dimethyl dichlorosilane, poly(ethylene glycol) (weight‐average molecular weight ～ 200), and toluene 2,4‐diisocyanate and characterized with IR, ¹H‐NMR and ¹³C‐NMR, and gel permeation chromatography. The synthesized SiMPU oligomers, with different concentrations, formed IPNs within the epoxy resins (diglycidyl ether of bisphenol A). The resultant IPN products were cured with diaminodiphenyl sulfone, diaminodiphenyl ether, and a Ciba–Geigy hardener under various curing conditions. Various mechanical properties, including the lap‐shear, peel, and impact strength, were evaluated. The results showed that 15 phr SiMPU led to better impact strength of epoxy resins than the others without the deterioration of the tensile properties. The impact strength increased continuously and reached a maximum value (five times greater than that of the virgin resin) at a critical modifier concentration (20 phr). The critical stress intensity factor reached 3.0 MPa m^1/2 (it was only 0.95 MPa m^1/2 for the virgin resin). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1497–1506, 2003     

Glass fibre reinforced composites of triglycidyl-p-aminophenol

Glass fibre reinforced epoxy composites were fabricated from the matrix resins diglycidyl ether of bisphenol A (DGEBA) and triglycidyl-p-aminophenol (TGAP) using diethylene triamine as curing agent. The epoxy laminates were evaluated for their mechanical properties, dielectrical properties and chemical resistance. Significant improvement in fiexural strength but a slight deterioration in dielectrical properties were observed on incorporation of an epoxy fortifier into the resin system before fabricating the composites.