Effect of unfunctionalized and HNO3‐functionalized MWCNT on the mechanical and electrical performances of PEMFC bipolar plates

This study aims at developing lightweight and high performance electrically conductive nanocomposites for proton exchange membrane fuel cell (PEMFC) bipolar plates (BPPs). These composites were made from an optimized co‐continuous mixture of Polyethylene terephthalate (PET) and polyvinylidene fluoride (PVDF) reinforced with highly conductive carbon additives composed of carbon black (CB) and synthetic graphite (GR). Multiwall carbon nanotubes (MWCNT) were functionalized then used to improve BPPs electrical conductivity and their mechanical properties, such as flexural and impact strengths. It was observed that the best BPP prototype was obtained using nitric acid (HNO₃)‐functionalized MWCNT. The latter led to the smothest BPP surface, the lowest through‐plane resitivity (0.12 Ω cm) and the highest impact and flexural strengths. These results are attributed to the improved dispersion of the functionalized MWCNT, a result of their best compatibilization with the (PET/PVDF) polymeric phase. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43624.     

Polyvinylidene fluoride/poly(ethylene terephthalate) conductive composites for proton exchange membrane fuel cell bipolar plates: Crystallization,structure, and through‐plane electrical resistivity

Polyvinylidene fluoride/poly(ethylene terephthalate) (PVDF/PET)‐based composites for proton exchange membrane fuel cell bipolar plates (BPs) were prepared at different crystallization temperatures and characterized by X‐ray diffraction, differential scanning calorimetry, and resistivity setup. Composite conductivity was made possible by using a mixture of carbon black (CB) and graphite (GR). To improve composite processability, its viscosity was reduced by adding a small amount of cyclic butylene terephthalate (c‐BT) oligomer and thermoplastic polyolefin elastomer. In the PVDF/PET‐based composite, it was found that PVDF phase could crystallize easily but PET crystallization was difficult. Because of the CB/GR additives, the formed crystals in PVDF/PET phases had a poor perfection degree and showed a lower melting temperature when compared with pure PVDF and PET. It was observed that PET nucleation was accelerated but not that of PVDF. According to through‐plane resistivity results, composite crystallization temperature range was divided into two parts (below/above 170°C), in which a different variation behavior of through‐plane resistivity was observed. It has been proved that the resistivity was mainly governed by the network of CB/GR developed inside the PET phase, and decreasing the crystallinity of PET led to a decrease of through‐plane resistivity, which is desirable for BPs. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Development and Characterisation of Electrically Conductive Polymeric‐Based Blends for Proton Exchange Membrane Fuel Cell Bipolar Plates

The main objective of this work was to develop films with controlled dimensions for proton exchange membrane fuel cell (PEMFC) bipolar plates (BPPs) using the twin‐screw extrusion process. These films consisted of a low‐viscosity polyethylene terephthalate (PET) in which a mixture of high specific surface area carbon black (CB) and synthetic flake graphite (GR) were dispersed. A third conductive additive, consisting of silver‐coated glass particles (SCG) or multi‐walled carbon nanotubes (MWCNT), was also added at a low concentration (5 wt.‐%) in order to study its synergistic effect on the PET‐based blend electrical conductivity. As the developed blends had to meet properties suitable for PEMFC bipolar plate applications, they were characterised for their electrical through‐plane resistivity, mechanical properties and oxygen permeability. Through‐plane electrical resistivity of about 0.3 Ω·cm and oxygen permeation rate of 3.5 × 10^–8 cc cm^–2 s^–1 were obtained for only 30 wt.‐% of a 60:40 mixture of CB/GR conductive additives. Although the substitution of 5 wt.‐% of CB/GR by the same amount of MWCNT had no significant effect on BPPs' electrical resistivity, it helped to improve their mechanical properties and especially their oxygen permeation, which was decreased from 3.5 × 10^–8 cc cm^–2 s^–1 to around 0.6 × 10^–8 cc cm^–2 s^–1.     

热处理对PVDF复合体系形态及性能的影响

利用ＤＳＣ、ＷＡＸＤ和ＳＥＭ等测试手段，研究了不同热处理条件下聚偏二氯乙烯合金／炭黑导电复合体系的结晶形态及正温度系数效应特性。结果表明，热处理可以改善基体结晶行为。使结晶度提高，从而使导电复合体系的室温电阻率下降、ＰＴＣ强度提高、ＰＴＣ曲线的重复稳定性变好。     

PET/PE/CB导电母料的研制

采用分离喂料技术在聚对苯二甲酸乙二酯(PET)/聚乙烯(PE)共混物中加入导电炭黑(CB),通过布斯往复式脉动挤出机熔融共混、挤出造粒,制备了综合性能较好的纤维级PET/PE/CB导电母料。研究发现,以PET/PE不相容共混物代替PET作母料的基体树脂,能以较低的CB用量获得较好的导电性能;CB的质量分数为15%时,母料的体积电阻率随PET用量的增加呈先减小后增大的趋势,在PET与PE的质量比为60∶40时,母料的体积电阻率最低。     

Thermo‐electric behavior (PTC) of carbon black–containing PVDF/UHMWPE and PVDF/XL‐UHMWPE blends

This paper describes the structure and electrical performance of PTC/NTC (positive temperature coefficient/negative temperature coefficient) effects and their reproducibility upon healing/cooling cycles. The following three‐component blends were studied: PVDF/UHMWPE/CB, PVDF/XL‐UHMWPE/CB and γ‐irradiated compression molded plaques of these blends. Carbon black (CB) particles are attracted to the UHMWPE (ultra high molecular weight polyethylene) and XL (cross‐linked)UHMWPE particles, which constitute the dispersed phase in the PVDF (polyvinylidene fluoride) matrix, but practically cannot or only very slightly penetrate them because of their extremely high viscosity. A double‐PTC effect was exhibited by all unirradiated samples. Irradiation of compression molded PVDF/UHMWPE/CB plaques does not add to their already outstanding reproducibility, and it results In a wide single‐PTC effect. Irradiation of compression molded PVDF/XL‐UHMV/PE/CB plaque, slabilizes their structure upon heating/cooling cycles and thus makes them reproducible PTC/NTC materials, still exhibiting a double‐PTC effect. The carbon black concentrations studied in this report are extremely low (< 2 phr CB) in comparison to other literature reports.     

Carbon black filled PET/PMMA blends: Electrical and morphological studies

In this work, the electrical and morphological properties of blends of poly(ethylene terephthalate) (PET), poly(methyl methacrylate) (PMMA), and carbon black (CB) were analyzed. Resistivity decreases similarly in both PET and PMMA with CB concentration. Similarly in the PET/PMMA blend, extensive modification to this behavior occurs, since resistivity becomes a function of morphology and specific location of CB in the polymers. A minimum in the resistivity of the blend with 5% CB (PET basis) is observed at 100% PET, whereas with an increase in the CB content to 20%, the minimum in the resistivity shifts to 60% PET. High conductivity is observed when PET is the continuous phase (having the larger viscosity). Large stresses lead to a large dispersion of CB and a high deformation and rupture of the dispersed PMMA phase. This situation itself promotes an increase of surface area of droplets and high CB concentrations at the interface. Consideration is given to models that predict a selective location of conductive particles in the PET matrix based on its lower interfacial tension with CB.     

Poly(butylene terephthalate)/ poly(ethylene‐co‐alkyl acrylate)/ carbon black conductive composites: Influence of composition and morphology on electrical properties

Poly(butylene terephthalate)/Poly(ethylene‐co‐alkyl‐acrylate)/carbon black (PBT‐EXA‐CB) blends, prepared through extrusion, were characterized as electrical conductive materials. In the composition range studied (55 ≤ PET % ≤ 75 w/w 5.5 ≤ CB % ≤ 11.1 w/w), various conductive behaviors were observed depending mainly on composition and poly(olefin) crystallinity. The observed positive temperature coefficient (PTC) is quite small compared to poly(olefin)‐CB systems, and our blends do not present a negative temperature coefficient (NTC) on complete melting of the CB‐containing phase, thus offering new possibilities for a regular electric power control. Volume expansion of both PBT and EXA was postulated to be the main parameter responsible for the thermal resistivity evolution through the range +20 to +170°C. A double‐percolation system between both the co‐continuous polymer phases and CB‐particles included in the poly(olefin) phase is postulated to explain these results.     

Carbon black‐filled PET/HDPE blends: Effect of the CB structure on rheological and electric properties

The rheological and electric properties of blends of poly(ethylene terephthalate) (PET) and high‐density polyethylene (HDPE) filled with various types of carbon black (CB) were analyzed in detail in this project. Four types of CB samples with available values of surface area, particle size, porosity, density, and maximum packing fraction were considered. Blends were prepared using an internal mixing chamber at two different rotational speeds, prior to mold compression of the samples. The rheological properties of the blends with varying polymer composition and a constant amount of CB were recorded in terms of torque variation with time for two shear rates (in terms of rotational speed). Rheological data were related to the resistivity of blends. Results show that the CB structure (porosity, surface area, apparent bulk density, and particle size) largely determine the resulting equilibrium torque and electrical properties. Furthermore, since CB is preferentially located in the HDPE phase, higher conductivity is observed as the PET content decreases, since the relative CB content in this phase increases. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 562–569, 2001     

VGCF填充PVDF/PMMA复合材料导电性能的研究

以气相生长碳纤维（VGCF）为导电填料,聚偏氟乙烯（PVDF）、聚甲基丙烯酸甲酯（PMMA）为基体制备复合型导电高分子材料。考察了填料用量、基体种类、配比以及PVDF结晶行为对复合材料导电性能的影响。结果表明,VGCF填充PMMA、PVDF、PVDF／PMMA（50／50）体系的渗滤阔值分别为5、4、3phr的填料用量。VGCF的加入会导致PVDF／PMMA体系发生微观相分离,而且VGCF会选择性富集在PVDF的非晶相中,所以PVDF／PMMA／VGCF体系的导电性呈现双重渗滤现象,该体系的体积电阻率不仅取决于富集相中VGCF的含量,而且还与PVDF相的连续性及其结晶行为密切相关。     

界面增强型PVDF/PET膜的制备及性能

通过对支撑材料进行表面改性处理和浸入凝胶法制备了界面增强型聚偏氟乙烯/聚对苯二甲酸乙二醇酯（PVDF/PET）超滤膜。用电导率在线测量法确定了硅烷偶联剂 3-氨丙基三乙氧基硅烷（KH550）水解液的制备条件,考察了改性处理条件对PVDF/PET膜的界面性能和力学性能的影响。通过180°剥离试验测试PVDF膜与支撑层间的剥离强度,用扫描电镜观察PET无纺布及PVDF膜破坏底面的微观形貌,用傅里叶红外光谱仪表征PET表面化学组成。结果表明,水解液中KH550用量较少时（≤3%）,处理时间延长,PVDF/PET间的剥离强度增大,水解液中KH550用量较多时（>3%）,处理时间延长,PVDF/PET间的剥离强度先增大后减小;PVDF/PET膜的拉伸强度随水解液中KH550用量的增加或处理时间的延长先增大后略减小。改性前后PVDF/PET膜的分离与透过性能对比表明,PET表面改性后,PVDF膜的牛血清白蛋白（BSA）截留率几乎不受影响,水通量略增。     

Characterization of carbon black‐filled immiscible polypropylene/polystyrene blends

The electrical and rheological behaviors of carbon black (CB)‐filled immiscible polypropylene (PP)/polystyrene (PS) blends were investigated. The compounding sequence influences the phase morphology of the ternary CB/PP/PS composites and the distribution of CB aggregates. Simultaneous measurements of resistance and dynamic modulus were carried out to monitor the phase coalescence of the ternary composites and CB migration and agglomeration in the PS phase during annealing at temperatures above the melting point of PP. The variation of resistivity is mainly attributed to CB agglomeration in the PS phase and the interfacial region, while the variation of dynamic modulus is regarded as the superimposition of the phase coalescence and CB agglomeration in the PS phase. The ternary composites with the majority of CB particles distributed in the interfacial region show the lowest conductive percolation threshold and the most stable resistivity–temperature performance during heating–cooling cycles. Copyright © 2011 Society of Chemical Industry     

Evaluation of Ni‐Mo and Ni‐Mo‐P Electroplated Coatings on Stainless Steel for PEM Fuel Cells Bipolar Plates

Stainless steel bipolar plates (BPPs) are the preferred choice for proton exchange membrane fuel cells (PEMFCs); however, a surface coating is needed to minimize contact resistance and corrosion. In this paper, Ni–Mo and Ni–Mo–P coatings were electroplated on stainless steel BPPs and investigated by XRD, SEM/EDX, AFM and contact angle measurements. The performance of the BPPs was studied by corrosion and conduction tests and by measuring their interfacial contact resistances (ICRs) ex situ in a PEMFC set‐up at varying clamping pressure, applied current and temperature. The results revealed that the applied coatings significantly reduce the ICR and corrosion rate of stainless steel BPP. All the coatings presented stable performance and the coatings electroplated at 100 mA cm⁻² showed even lower ICR than graphite. The excellent properties of the coatings compared to native oxide film of the bare stainless steel are due to their higher contact angle, crystallinity and roughness, improving hydrophobicity and electrical conductivity. Hence, the electroplated coatings investigated in this study have promising properties for stainless steel BPPs and are potentially good alternatives for the graphite BPP in PEMFC.     

Morphology and electrical properties of carbon black/poly(ethylene terephthalate)/polypropylene composite

This work attempts to develop a carbon black (CB) filled conductive polymer composite based on poly(ethylene terephthalate) (PET) and polypropylene (PP). The process follows by localizing the CB particles in the minor phase (PET), and then the conductive masterbatch was elongated to form conductive microfibrils in PP matrix during melt extrusion process. After compression molding, a fine conductive three‐dimensional microfibrillar network is constructed. For comparison purpose, CB, PET, and PP are mixed using different pattern. The morphology and the volume resistivity of the obtained composites are evaluated. Electrical conductivity investigation shows that the percolation threshold and resistivity values are dependent on the CB concentration. The best morphological observation shows that the PET phases forms well‐defined microfibrils, and CB particles overwhelmingly localize in the surfaces of the PET microfibrils, which led to a very low percolation threshold, i.e., 4.5 phr, and a reasonable conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electrically conductive in situ microfibrillar composite with a selective carbon black distribution: An unusual resistivity-temperature behavior upon cooling

Carbon black (CB) filled electrically conductive in situ microfibrillar poly(ethylene terephthalate) (PET)/polyethylene (PE) composites (FCMC) with CB particles selectively localizing at the surfaces of PET microfibrils were successfully prepared through a slit die extrusion-hot stretch-quenching process. Resistivity-temperature behaviors of the FCMC samples were studied systematically during heating-cooling runs (HCR) with different top test temperatures. When the top test temperature was set as 140 °C, the resistivity abnormally increased during cooling below 100 °C, showing the cooling-induced resistivity increase. The room-temperature resistivity after one heating-cooling run was 4 orders of magnitude higher than that of the original samples. Thermal residual stresses developed in the interfaces between PET microfibrils and PE matrix were responsible for the cooling-induced resistivity increase, which led to the damage of the conductive network. The top test temperature dominated the cooling-induced resistivity increase of FCMC. There was a critical temperature, 150 °C, above which the cooling-induced resistivity increase disappeared. A model was proposed to illustrate this cooling-induced resistivity increase.     

碳黑系聚酯导电母粒的研究

分别将未处理的碳黑和经钛酸酯偶联剂处理后的碳黑与聚酯切片混合后,经双螺杆熔融共混,制备了纤维级导电母粒。研究了钛酸酯偶联剂的作用机理和钛酸酯偶联剂用量对母粒导电性能和流变性能及所得纤维力学性能的影响。结果表明:偶联剂的加入起到了内增塑的作用,降低了母粒的表观黏度,适当的偶联剂用量可用于设计和制备具有低突增界限浓度的导电母粒。     

热历史对LLDPE／EVA／CB导电材料PTC性能的影响

研究了淬火（液氮冷却）,空气自然冷却,空冷后退火,水冷,缓慢冷却等不同热历史条件下LLDPE／EVA／CB导电复合材料的PTC（正温度系数）特性,并借助DMA,DSC,SEM,TEM等手段揭示了LLDPE／EVA／CB导电复合材料PT特性与结晶形态等结构间的关系。结果表明,LLDPE／EVA／CB导电复合材料的PTC行为受结晶度和结晶形态影响很大,结晶度愈高,室温电阻愈小,PTC强度愈高;结晶形态愈复杂,从室温至PTC转变温度的低温PTC效应愈强,熔体缓慢冷却及退火工艺,可提高复合物结晶度,降低取向作用,使电阻率下降。     

Effect of coupling agent on structure and properties of micro–nano composite fibers based on PET

Poly(ethylene terephthalate) (PET)/carbon black (CB) micro–nano composite fibers were manufactured by melt spinning method. To achieve good dispersion, nano‐CB particles were modified by coupling agent (CA). The effect of CA on structure and properties of the fibers were investigated via scanning electron microscopy (SEM), tensile testing, differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), sonic orientation, and birefringence, respectively. At 2 wt % CA dosage, CB particles present the optimal dispersion in the fibers, shown in SEM images. Besides, the fibers possess the maximum breaking strength, the lowest crystallization temperature, and the highest crystallinity. After CA modification, the superior interfacial structure between PET and CB is beneficial to improve mechanical properties of the fibers. The well dispersed CB particles provide more heterogeneous nucleation points, resulting in the highest crystallinity. Furthermore, the fibers with 2 wt % CA dosage possess the maximum orientation and shrinkage ratio. According to Viogt–Kelvin model, the thermal shrinkage curves of the fibers can be well fitted using single exponential function. The three‐phase structure model of crystal phase–amorphous phase–CB phase was established to interpret the relationship among shrinkage, orientation, and dispersion of CB particles. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43846.     

Effect of TEP content in cooling bath on porous structure,crystalline and mechanical properties of PVDF hollow fiber membranes

Poly (vinylidene fluoride) (PVDF) hollow fiber membranes were prepared by adding triethyl phosphate (TEP) to the cooling water bath in a modified thermally induced phase separation process. The effect of TEP content in the cooling bath on the porous structure, crystallinity, thermal and mechanical properties of PVDF hollow fiber membranes was investigated. The melting temperature and crystallinity of the membranes were determined using differential scanning calorimetry. The crystalline and cross‐section morphology of the hollow fiber membranes were investigated using wide angle X‐ray diffraction and scanning electron microscopy. The resulting membrane exhibited a nearly symmetric structure. The results showed that the TEP content in the cooling bath had a crucial role on the membrane formation, which was also confirmed from the morphology and mechanical properties of the hollow fibers. The porosity, average pore size, crystallinity, Young's modulus, max stress, and elongation at breakage of the hollow fiber membranes can be related to the amount of TEP in the cooling bath. Better pore connectivity was obtained in hollow fiber membranes when the weight ratio of TEP to water was 40:60. POLYM. ENG. SCI., 54:2207–2214, 2014. © 2013 Society of Plastics Engineers     

Structure and properties of melt‐spun PET/MWCNT nanocomposite fibers

Polyethylene terephthalate (PET) melt‐spun fibers were modified with multiwall carbon nanotubes (MWCNT) to obtain conductive microfibers smaller than 90 μm in diameter. Physical properties such as crystallinity and orientation of as‐spun fibers were studied by X‐ray diffraction, Raman spectroscopy, and microscopy techniques at different draw ratios (DR) and MWCNT concentrations. Morphological and orientation analysis of MWCNT after melt‐spinning process showed agglomerates formation and highly oriented CNTs. The study of the orientation of PET crystalline phase in drawn fibers proved that the addition of nanoparticles decreases the orientation of crystalline units inside the fibers. The orientation of MWCNT as well as that of PET chains was studied using Raman spectroscopy at different DR and a high degree of CNT orientation was observed under high DR conditions. Mechanical and electrical properties of as‐spun fibers were also investigated. Our results showed that it was possible to achieve conductive fibers at a MWCNT concentration of 2% w/w, and more conductive fibers using higher DR were also obtained without increasing the MWCNT concentration. Mechanical properties results showed interestingly high value of maximum tensile strain at break (ε_max) of nanocomposite fibers, up to three times more than pure PET fibers. POLYM. ENG. SCI., 50:1956–1968, 2010. © 2010 Society of Plastics Engineers