Property evaluation and structure analysis of polyurethane/epoxy graft interpenetrating polymer networks

Polyurethanes obtained from 4,4′‐diphenylmethane diisocyanate (MDI) and polydiols with different molecular weights (polyethylene glycol and polyoxypropylene diols) were used as modifiers for diglycidyl ether of bisphenol A. Impact strength (IS), critical stress intensity factor (K_C), flexural strength and flexural strain at break were measured as a function of polyurethane (PUR) type and content. Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and infrared spectroscopy (FTIR) were employed for the structure and morphology analysis. It was found that the addition of polyurethane with an excess of isocyanate groups to epoxy resin resulted in the formation of a grafted interpenetrating polymer network structure. The mechanical properties of epoxy resin were improved with 5 and 10% PUR. Moreover, it was observed that composites containing PUR based on higher molecular weight (PUR 1002 and PUR 2002) with long flexible segments exhibited higher impact strength while PUR prepared from polyethylene glycol had a higher flexural energy to break and a higher flexural modulus. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

不同原料对合成PUR弹性体性能的影响

采用相同官能度、不同分子量的聚醚多元醇和甲苯二异氰酸酯(TD I)及扩链剂反应合成了系列聚氨酯(PUR)弹性体,同时对所合成的PUR弹性体进行了表征。结果表明,聚醚多元醇的相对分子质量对PUR弹性体的性能有较大影响,相对分子质量越大,柔性链段含量就越多,弹性体的拉伸强度、断裂强度和硬度就减小,断裂伸长率则相对提高。同时也进一步证明了软硬链段之间的均匀分布和较强的相互作用更有利于弹性体力学性能的提高。     

Preparation and characterization of an epoxy resin modified by a combination of MDI‐based polyurethane and montmorillonite

The present work investigates the modification of epoxy resin by using a combination of nanoclay (montmorillonite—Cloisite 30B) and a liquid polymeric modifier (polyurethane). Polyurethane was obtained from 4,4′‐diphenylmethane diisocyanate and polydiols with different molecular weight: polyethylene glycol (PEG 400) and polyoxypropylene diols with molecular weight 1000 g/mol and 2000 g/mol. The impact strength, the critical stress intensity factor as well as the flexural strength were evaluated as functions of modifiers content. The obtained results showed that hybrid composites exhibit enhanced mechanical properties without significant changes of the glass transition temperature. FTIR analysis showed that chemical reactions took place between the hydroxyl groups of epoxy resin and the isocyanate groups of polyurethane, explaining an improvement of the mechanical properties of epoxy resin. However, XRD results demonstrated the formation of an exfoliated structure for the hybrid compositions with both polyurethane and montmorillonite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical properties of epoxy resin modified with polycarbonate and reactive polybutadiene

Epoxy resin Epidian 5 cured with triethylene tetramine was modified with hydroxyl‐terminated polybutadiene (PB) and polycarbonate (PC). Compositions with different amount of modifiers were obtained and tested for their impact strength, flexural strength, as well as resistance to crack propagation. The latter was assessed by evaluating the critical stress intensity factor under three‐point bending mode using single‐edge notched specimens. Scanning electron microscopy was used to analyze the fractured sample surfaces. The obtained results revealed that the mechanical properties of epoxy resin were improved due to the formation of heterogeneous phase with rubber particles, which arrest the propagation of cracks. Moreover, synergism effect was observed with the hybrid composition containing 10% PC and 2.5% of reactive PB. The impact strength was higher by ～ 15% than the sum of impact strength of compositions containing only one modifier. Another hybrid composition with 2.5% PB and 2.5% PC also exhibited synergism effect with the flexural strain at break, the energy at break under flexure, as well as the brittle fracture energy estimated from the critical stress intensity factor measurements. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Molecular modeling of cellulose in amorphous state part II: effects of rigid and flexible crosslinks on cellulose

It is essential to understand the molecular level response of crosslinked cellulose chain segments upon deformation, in order to develop new agents which convey high durable-press (DP) rating to cellulose fibers with minimal strength loss. In this work models of amorphous cellulose crosslinked with both rigid and flexible crosslinks were constructed computationally for this purpose. Rigid crosslinks bound cellulose molecular segments together and blocked the chain slippage, providing cellulose models with a higher initial modulus and better elastic response. However, the loss of the chain slippage led to stress being distributed unevenly among cellulose chains. Chains in some regions were subjected higher stress and these regions were opened up much more than the rest of the cellulose, which presumably caused models to fail. When conformationally flexible crosslinks were used, breaking strain of cellulose was not significantly reduced but deformation recovery was not improved either, in comparison with the models of untreated cellulose. Conformational transitions were observed in the flexible crosslinks during extension. These results help to explain how and why rigid crosslinks work to provide wrinkle resistant properties and why they also lower tensile strength, and that just using a conformationally flexible crosslinking will not provide any recovery.     

Polyurethane Composites Reinforced with Walnut Shell Filler Treated with Perlite,Montmorillonite and Halloysite

In the following study, polyurethane (PUR) composites were modified with 2 wt.% of walnut shell filler modified with selected mineral compounds–perlite, montmorillonite, and halloysite. The impact of modified walnut shell fillers on selected properties of PUR composites, such as rheological properties (dynamic viscosity, foaming behavior), mechanical properties (compressive strength, flexural strength, impact strength), dynamic-mechanical behavior (glass transition temperature, storage modulus), insulation properties (thermal conductivity), thermal characteristic (temperature of thermal decomposition stages), and flame retardant properties (e.g., ignition time, limiting oxygen index, heat peak release) was investigated. Among all modified types of PUR composites, the greatest improvement was observed for PUR composites filled with walnut shell filler functionalized with halloysite. For example, on the addition of such modified walnut shell filler, the compressive strength was enhanced by ~13%, flexural strength by ~12%, and impact strength by ~14%. Due to the functionalization of walnut shell filler with thermally stable flame retardant compounds, such modified PUR composites were characterized by higher temperatures of thermal decomposition. Most importantly, PUR composites filled with flame retardant compounds exhibited improved flame resistance characteristics-in all cases, the value of peak heat release was reduced by ~12%, while the value of total smoke release was reduced by ~23%.     

Effects of the interfacial stress-induced crystallization on the matrix crystalline morphology and the mechanical properties of glass fiber-reinforced high density polyethylene composites

In the melt-mixing process of high density polyethylene (HDPE) and glass fibers (GF), four types of composites with various interfacial bond strength were obtained by adding maleic low molecular weight polyethylene (MPEW) or maleic anhydride (MAH) and initiator, etc. The mechanical properties of these composites and their dependence on the matrix crystalline morphology were investigated by scanning electron microscopy, small-angle light scattering, differential scanning calorimetry, wide-angle X-ray diffraction, and a material universal mechanical testing machine. The occurrence of the interfacial transition regions made of extended-chain crystals around glass fibers was found to be the result of crystallization effects induced by the interfacial stress. The interfacial stress was mainly produced from the matrix shrinkage in the specimen molding process. Under high interfacial bond strength conditions, the forming process of the extended-chain crystals was found to both relax the interfacial stress and at the same time, enhance the interfacial phase modulus and improve the mechanical properties of the composites. Under a 30% glass fiber content condition, the extended-chain crystals formed along the normal direction of glass fiber surfaces connected with each other, fully filled the matrix, and led to a significant increase in the Charpy impact strength of the composites. By contrast, under weak interfacial adhesion, the interfacial stress was released by a dewetting process of the interfacial phase and by the formation of interfacial cracks. Consequently, the interfacial stress did not influence the growth of the spherulites in the matrix and at the same time, the Charpy impact strength of the composite was lower.     

Mechanical properties and creep behavior of poly(trimethylene terephthalate)/mesoporous silica composites

The poly(trimethylene terephthalate) (PTT) containing mesoporous silica (SBA‐15) prepared by in situ polymerization were used as the master batch in this work and mixed with the commercial PTT to fabricate PTT/mesoporous silica composites. The mechanical properties and viscoelastic behaviors such as creep and creep recovery of as‐obtained composite system were then studied in detail. The results reveal an evident reinforcing effect of the mesoporous SBA‐15 particles at the lower loading levels. Compared with those of the pure PTT, the tensile strength and impact strength of the composite with 0.5 wt% SBA‐15 particles increase by about 26% and 10%, respectively. This is attributed to the physical crosslinking between SBA‐15 and PTT chain caused by the mesoporous structure of SBA‐15 particle, which is confirmed by the increased glass transition temperature of the composites relative to the pure PTT. At the higher loading levels, however, the presence of mesoporous particle reduces the overall strength of PTT because the concentration of lower molecular weight PTT in the master batch also increases with increasing loading of SBA‐15. Therefore, superfluous addition of master batch has negative contribution to the mechanical strength of PTT composites. Besides, the composite system presents the higher creep levels and the lower recovery rates than the pure PTT, indicating that the presence of mesoporous SBA‐15 particles restrains the movements of PTT chain segments during creep and creep recovery. This is further confirmed by the viscoelastic model predictions. POLYM. COMPOS., 36:1386–1393, 2015. © 2014 Society of Plastics Engineers     

New linear polyurethaneureas based on polyoxytetramethylene,aliphatic diisocyanates,and aromatic diamines

New polyurethaneureas have been synthesized with α-ω hydroxylated polyoxytetramethylene, aliphatic diisocyanates and nonhalogenated aromatic diamines. Four series of PUR have been studied by varying the PTMO molecular weight, the stoichiometry, the nature of the aliphatic diisocyanate, and the steric hindrance of the aromatic diamine. Quantitative evaluation of the degree of phase separation was obtained by DSC. An estimation of the dispersed soft segments outside the soft phase could thus be made. In addition to DSC, dynamic mechanical properties, were obtained for the four series of PUR over a wide temperature range. The hard segments in the PUR chains are amorphous and their high temperature behavior depends only on the strength of interactions in the amorphous state. Finally, stress-strain measurements were carried out on a few samples, and a wide range of tensile properties has been observed.     

高性能聚氯乙烯复合材料的研究

以聚氯乙烯(PVC)为基体、热塑性聚氨酯弹性体(PUR–T)为增韧剂、连续玻璃纤维(GF)为增强剂,通过熔体浸渍挤出工艺制备高性能PVC复合材料,并对其力学性能、耐热性能和动态力学性能进行研究。结果表明,随着PUR–T或连续GF含量增加,复合材料的力学性能和耐热性能均得到提高,当PUR–T/PVC质量比为2/8,连续GF质量分数为30%时,复合材料的拉伸强度、缺口冲击强度、弯曲强度、弯曲弹性模量、维卡软化温度分别为83.42 MPa,19.81 k J/m2,106.33 MPa,8 823.36 MPa和74.1℃;随着连续GF含量增加,复合材料的储能模量和玻璃化转变温度提高,损耗因子降低;扫描电子显微镜测试结果表明连续GF在PVC中保持了较长的长度,分散性良好。     

Mechanically Strong Polyurethane Composites Reinforced with Montmorillonite-Modified Sage Filler (Salvia officinalis L.)

Rigid polyurethane (PUR) foams reinforced with 1, 2, and 5 wt.% of salvia filler (SO filler) and montmorillonite-modified salvia filler (MMT-modified SO filler) were produced in the following study. The impact of 1, 2, and 5 wt.% of SO filler and MMT-modified SO filler on the morphological, chemical, and mechanical properties of PUR composites were examined. In both cases, the addition of 1 and 2 wt.% of SO fillers resulted in the synthesis of PUR composites with improved physicomechanical properties, while the addition of 5 wt.% of SO fillers resulted in the formation of PUR composites with a less uniform structure and, therefore, some deterioration in their physicomechanical performances. Moreover, the results showed that the modification of SO filler with MMT improved the interphase compatibility between filler surface and PUR matrix. Therefore, such reinforced PUR composites were characterized by a well-developed closed-cell structure and improved mechanical, thermal, and flame-retardant performances. For example, when compared with reference foam, the addition of 2 wt.% of MMT-modified SO filler resulted in the formation of PUR composites with greater mechanical properties (compressive strength, flexural strength) and improved dynamic-mechanical properties (storage modulus). The PUR composites were characterized by better thermal stability as well as improved flame retardancy—e.g., decreased peak rate of heat release (pHRR), reduced total smoke release (TSR), and increased limiting oxygen index (LOI).     

Toughening of Epoxy with Preformed Polyethylene Thermoplastic Filler

The potential of polyethylene as a thermoplastic filler towards improving the fracture properties of epoxy resin was explored. Oxo-degradable films were subjected to thermo-oxidative exposure, and the oxidized polyethylene (OPE) was extracted with acetone to remove low molecular weight products (APE). The presence of functionalities led to its homogenous dispersion in the epoxy matrix. Blending of epoxy with OPE and APE led to significant improvement in both quasi-static and impact properties, as evidenced by 44% increase in G_IC and 21% increase in impact strength at loadings of 3% w/w. The strain rate sensitivity of the composites was also investigated.     

碳纳米管/聚氨酯复合材料的粘接性能

利用超声分散、酸处理以及表面活性剂分散的方法将碳纳米管分散到蓖麻油中,制备了蓖麻油型聚氨酯/碳纳米管(PUR/CNTs)复合材料,观察了该复合材料的微观结构,探讨了CNTs用量、酸处理时间以及表面活性剂的用量对复合材料粘接性能的影响。结果表明,随着蓖麻油中CNTs用量的增加,该复合材料的粘接强度不断提高,当增加到2%时,粘接强度提高84.4%;硝酸处理3 h的聚氨酯/碳纳米管复合材料的粘接强度最大,比未酸处理的复合材料增加15%;表面活性剂分散的聚氨酯/碳纳米管复合材料的粘接强度能得到进一步的提高。     

PEG/PCL基复合软段降解型PUF力学与动态力学特性研究

采用一步法制备了聚乙二醇/聚己内酯（PEG/PCL）复合软段聚氨酯泡沫塑料（PUF）,研究了PEG/PCL复合软段配比、软段相对分子质量等对PUF力学性能和动态力学性能的影响。结果表明,无论是采用相对分子质量为400还是相对分子质量为1000的PEG与PCL-210N复合,随软段中PCL含量的增大,材料的拉伸强度、断裂伸长率、定应变应力均提高;随着PEG相对分子质量的增大,材料的断裂伸长率提高,拉伸强度、定应变应力降低;玻璃化转变温度（Tg）顺序为Tg（PEG400）> Tg（PCL210N）> Tg（PEG1000）。     

聚醚型聚氨酯弹性体的合成及其动态力学行为

采用两步合成法,以4,4′-二苯基甲烷二异氰酸酯(MDI)和1,4-丁二醇(BDO)为硬段,相对分子质量分别为1000、2000、4000的聚氧化丙烯二元醇(PPG)为软段,制备了一系列聚醚型聚氨酯(PUR)弹性体,研究了预聚体异氰酸酯指数R及软段相对分子质量对PUR动态力学性能的影响。结果表明,预聚体R值增大,即PUR的硬段含量增加,储能模量G′提高,软段相的玻璃化转变温度(Tg)升高,软硬相区的相容性增大;软段相对分子质量增加,PUR的G′下降,软段相的Tg降低,并出现硬段相的玻璃化转变,软硬相区的相分离程度增大。     

Novel polyurethane elastomer continuous carbon fiber composites: Preparation and characterization

Preparation and characterization of novel polyurethane (PUR)–carbon fiber (CF) composites are reported. The reinforcement of PUR elastomers was achieved using unidirectional continuous CFs with different coatings (uncoated and epoxy and polyester resin coatings) by applying molding for the preparation of PUR‐CF composites. Considerable reinforcement of PUR was attained even at relatively low CF content, e.g., maximum stress and Young's modulus of PUR‐CF composite at CF content 3% (m/m) were found to be 3–5 and 4–10 times higher than those of the PUR‐matrix, respectively. In addition, a linear relationship between the Young's modulus and the CF content was found as well as linear variation of maximum stress with the CF content was also observed. The adhesion of CF to the PUR‐matrix was strong in each case as concluded from the strain–stress and the scanning electron microscopy (SEM) investigations. However, the extent of reinforcement of PUR at a given CF content was found to depend greatly on the coatings of CF, and increased in the following order: epoxy resin < polyester resin < uncoated. The effect of the coating of CF on the reinforcement of PUR is also discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 287–292, 2007     

柔性成膜剂和附加剪切场对GF/PP结构与性能的影响

利用自制的可控剪切应力场装置,连接在熔融挤出机料筒末端,使复合材料熔体在成型过程中,受到可控的附加剪切应力场作用,试验成膜剂和附加剪切场对玻纤增强PP复合材料界面结构与性能的作用。结果表明:在成型加工过程中,附加剪切场会改变GF/PP复合材料界面结构,其变化程度与玻纤处理工艺有关,柔性成膜剂有稳定复合材料界面结构和提高GF/PP复合材料力学强度的作用;在所用3种成膜剂中,POE效果最佳,PUR其次,K树脂较差。     

Biobased Polyurethane Composite Foams Reinforced with Plum Stones and Silanized Plum Stones

In the following study, ground plum stones and silanized ground plum stones were used as natural fillers for novel polyurethane (PUR) composite foams. The impact of 1, 2, and 5 wt.% of fillers on the cellular structure, foaming parameters, and mechanical, thermomechanical, and thermal properties of produced foams were assessed. The results showed that the silanization process leads to acquiring fillers with a smoother surface compared to unmodified filler. The results also showed that the morphology of the obtained materials is affected by the type and content of filler. Moreover, the modified PUR foams showed improved properties. For example, compared with the reference foam (PUR_REF), the foam with the addition of 1 wt.% of unmodified plum filler showed better mechanical properties, such as higher compressive strength (~8% improvement) and better flexural strength (~6% improvement). The addition of silanized plum filler improved the thermal stability and hydrophobic character of PUR foams. This work shows the relationship between the mechanical, thermal, and application properties of the obtained PUR composites depending on the modification of the filler used during synthesis.     

Effects of molecular weight and strain rate on the flexural properties of polycarbonate

The effects of changes in molecular weight (7000 to 22,000) and strain rate (0.0001 to 4 min.^?1) on the flexural properties of polycarbonate have been examined in detail with the use of speciments of different molecular weight prepared by high-energy electron irradiation. The results have been plotted as surfaces which show the dependence of both stress and strain on molecular weight and strain rate, and these surfaces have been described in terms of brittle, transitional, and ductile regions. The relationships between stress or strain and molecular weight in the brittle region have been shown to be hyperbolic. A single failure locus has been found to include all the corresponding stress and strain data obtained at the various molecular weights and strain rates. In the low strength region this locus exhibits a proportionality between stress and strain, while at high strength values, strain becomes a logarithmic function of stress. Stress–molecular weight data obtained at the various rates have been superimposed to form a single composite curve, and the corresponding crossplots of stress–log rate have been treated similarly. It is concluded from these superpositions that an equivalence exists between changes in both molecular weight and strain rate such that a tenfold change in strain rate corresponds approximately to a change of 1000 in molecular weight. Strain-strain rate data obtained at the various molecular weights have also been superimposed in a similar manner. Modulus is shown to increase slowly with decrease in molecular weight and appears to be relatively insensitive to changes in strain rate.     

Compatibilization of PUR/PVAC polymer blend by addition of calcium carbonate filler

The influence of untreated and stearic acid surface pretreated calcium carbonate (CaCO₃) nanofiller (U1 – untreated CaCO₃ and U1S2 – stearic acid treated CaCO₃) on the properties of polyurethane/poly(vinyl acetate) (PUR/PVAC) polymer blends was investigated. Adhesion between fillers and polymers in the polymer blend composite, and filler position in regard to the polymer phases, are predicted on the basis of calculated adhesion parameters and wetting factor ωa of PUR, PVAC, U1, and U1S2. U1 is located in the PUR matrix phase and U1S2 is located at the interface between matrix PUR domain and dispersed PVAC domain. Polymer blend composites with predominant U1S2 showed lower tensile strength and elongation compared to these of polymer blend composites with predominant U1 mainly due to the fillers' different surface properties, which confirmed that the mechanical properties of polymer blend composites were dependent on overall system morphology rather than the filler location. POLYM. COMPOS. 37:1274–1281, 2016. © 2014 Society of Plastics Engineers