An electrochemical immunosensor for ochratoxin A based on immobilization of antibodies on diazonium-functionalized gold electrode

A novel electrochemical immunosensor for sensitive detection of ochratoxin A (OTA) was reported. An electrochemical and chemical reaction protocol was elaborated to modify the gold electrode. A screen-printed gold electrode (SPGE) was modified with a layer of 4-nitrophenyl, assembled from 4-nitrophenyl diazonium salt synthesized in situ in acidic aqueous solution. Next, the nitro groups were electrochemically reduced to amines followed by activation with glutaraldehyde to give a stable intermediate derivative that covalently binds antibodies against OTA during the second step, thereby tailoring an immunosensor for ochratoxin A. The utility of the electrochemical immunosensor for a competitive immunoassay was demonstrated. A competition between OTA and fixed concentration of a horseradish peroxidase-labeled OTA (OTA-HRP) for the immobilized antibodies was realized. The activity of the bound OTA-HRP was electrochemically measured by chronoamperometry (CA) using 3,3′,5,5′-tetramethylbenzidine (TMB) as substrate. The immunosensor obtained using this novel approach enabled a detection limit of 12 ng mL⁻¹ and a dynamic range up to 60 ng mL⁻¹ of OTA. Precision, accuracy and stability studies were satisfactory for the developed immunosensor.     

Effects of nucleating agents on the morphologies and performances of poly(vinylidene fluoride) microporous membranes via thermally induced phase separation

The effects of nucleating agents on the morphology and performance of poly(vinylidene fluoride) (PVDF) microporous membranes via thermally induced phase separation were investigated. The nucleating agents studied were dicyclohexyl benzene amide (TMB‐5), 2,2‐methylene bis(4,6‐tertiary butyl phenol) sodium phosphate (TMP‐1), and 1,3 : 2,4‐di‐p‐methylbenzylidene sorbitol (DM–LO). Light transmittance experiments and differential scanning calorimetry (DSC) were performed to obtain phase diagrams of PVDF/tributyl citrate/di(2‐ethylhexyl) phthalate/nucleating agent doped solutions. The morphology and performance of the prepared PVDF microporous membranes were characterized with scanning electron microscopy and microfiltration experiments. The results show that the thermodynamics of liquid–liquid phase separation were not affected by the addition of the nucleating agents, but solid–liquid phase separation was influenced. The system with 0.3 wt % TMB‐5 had the fastest crystallization rate and a better nucleation ability. The PVDF microporous membranes had a partly closed, lacy bicontinuous structure with TMP‐1 and DM–LO, whereas the membrane with 0.3 wt % TMB‐5 had an interconnected bicontinuous structure. The pore size distribution became narrower with the addition of nucleating agent. With 0.3 wt % TMB‐5, the membrane had the minimum mean pore size (0.095 μm), a porosity of 80.3%, and a pure water flux of 270 L·m^?2·h^?1; these values were higher than those of the pure PVDF membrane. The performances of the membranes decreased with additions of TMB‐5 of greater than 0.3 wt %. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Open the Technical Black Box of Tumor Mutational Burden (TMB): Factors Affecting Harmonization and Standardization of Panel-Based TMB

As tumor mutational burden (TMB) has been approved as a predictive biomarker for immune checkpoint inhibitors (ICIs), next-generation sequencing (NGS) TMB panels are being increasingly used clinically. However, only a few of them have been validated in clinical trials or authorized by administration. The harmonization and standardization of TMB panels are thus essential for clinical implementation. In this review, preanalytic, sequencing, bioinformatics and interpretative factors are summarized to provide a comprehensive picture of how the different factors affect the estimation of panel-based TMB. Among the factors, poor DNA quality, improper formalin fixation and residual germline variants after filtration may overestimate TMB, while low tumor purity may decrease the sensitivity of the TMB panel. In addition, a small panel size leads to more variability when comparing with true TMB values detected by whole-exome sequencing (WES). A panel covering a genomic region of more than 1Mb is more stable for harmonization and standardization. Because the TMB estimate reflects the sum of effects from multiple factors, deliberation based on laboratory and specimen quality, as well as clinical information, is essential for decision making.     

用于疝气补片的PVDF涂层聚酯单丝的制备

采用在聚酯(PET)单丝表面涂覆上与人体组织基本不产生黏连、相容性好的聚偏氟二乙烯(PVDF)涂层,以此单丝为原料制成的疝气补片可防止黏连和感染现象。由于PET单丝很难直接在表面进行PVDF的涂覆,所以先对其表面进行碱减量处理,碱处理工艺为:NaOH溶液浓度4mol/L,处理温度90℃,时间2h。采用DSC、红外光谱、声速、干热与沸水收缩、接触角等测试手段对PVDF涂层的PET单丝结构与性能进行了表征。研究结果表明:PVDF的亲水性比PP好;PET单丝的取向度经碱处理后有所减小,但涂层后又有增加;涂层后的PET单丝热收缩率减小;涂层是物理涂层,PET和PVDF界面上无化学反应发生。     

Structure, phase transition and electric properties of poly(vinylidene fluoride-trifluoroethylene) copolymer studied with density functional theory

The geometry, energy, internal rotation, vibrational spectra, dipole moments and molecular polarizabilities of poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) of α- and β-chain models were studied with density functional theory at B3PW91/6-31G(d) level and compared with those of the poly(vinylidene fluoride) (PVDF) homopolymer. The chain length and the trifluoroethylene (TrFE) concentration were examined to discuss the copolymer chain stabilities, chain conformations and electric properties. The asymmetrical internal-rotation potential energy curve shows that the angles for the g and g′ conformations in the α-chain (tg and tg′) models are 53° and −70°, respectively, and the β-chain (ttt) conformation is a slightly distorted all-trans plane with dihedral angle at 177°. The energy differences, E_β − E_α(g) and E_β − E_α(g′), between the β- and the α-conformation are 2.1 and 7.8 kJ/mol, respectively. These values are smaller than that in PVDF (8.4 kJ/mol), suggesting that the β-conformation in the copolymer will be more stable than in PVDF. The energy barriers for β → α(g) and β → α(g′) transitions are 16.2 and 5.8 kJ/mol, respectively. The former is almost twice of the energy barrier in PVDF by 8.2 kJ/mol and the latter is slightly smaller (by 2.4 kJ/mol) than that in PVDF. The respective energy barriers for α(g) → β and α(g′) → β transitions are 18.3 and 13.6 kJ/mol compared with the value 16.3 kJ/mol in PVDF. The asymmetrical energy barriers may be one of the reasons for the copolymers with 0.5-0.6 (mole fraction) VDF exhibiting complicated phase transition behavior. The conformation of α-chain P(VDF-TrFE) exhibits from a helical (containing higher TrFE) to a nearly beeline (containing lower TrFE). This behavior is different from that in the PVDF and the nearly beeline conformation might be responsible for the increasing crystallizability. The helical might also be associated with the complicated phase transition behavior and the larger lattice strain in the P(VDF-TrFE)s with higher TrFE concentration. The energy difference per monomer unit between the β- and α-chain decreases with increasing TrFE content. The ideal β-chain is curved with a radius of about 30 Å, which is similar to that in PVDF. The chain curvature and the TrFE content will affect the dipole moment contribution per monomer. The chain length and TrFE content will not significantly affect the mean polarizability. The calculations indicated that there are some additional characteristic vibrational modes that may be used in identification of the α- or β-phase P(VDF-TrFE)s with different TrFE contents.     

Novel composites of copper nanowire/PVDF with superior dielectric properties

Novel copper nanowires (CuNWs)/poly(vinylidene fluoride) (PVDF) nanocomposites with high dielectric permittivity (ε′) and low dielectric loss (ε″) were prepared by a precipitation technique followed by melt compression. Their dielectric properties over the broadband frequency range, i.e. 10¹–10⁶ Hz, were compared with multi-walled carbon nanotubes (MWCNT)/PVDF nanocomposites prepared by the same technique. It was observed that the CuNWs/PVDF nanocomposites had higher dielectric permittivity, lower dielectric loss and thus significantly lower dissipation factor (tan δ) than the MWCNT/PVDF nanocomposites at room temperature. This behavior was ascribed to a higher conductivity of the fresh core of the CuNWs relative to the MWCNT, which provided the composites with a higher amount of mobile charge carriers participating in the interfacial polarization. Moreover, the presence of oxide layers on the CuNWs surfaces diminished the conductive network formation leading to a low dielectric loss.     

The effect of the soft segment of prepolymers on properties of poly(urethane‐ester) and its biodegradability

The influence of soft‐segment prepolymers prepared through the polymerization of δ‐valerolactone (VL) and 2,2‐dimethyl‐1,3‐propandiol (DP) monomers on the structure and properties of poly(urethane‐ester) as well as its biodegradability were investigated. Poly(urethane‐ester) was prepared in two steps. The first step was the preparation of prepolymers with various chain lengths by polymerizing VL and DP monomers in the presence of a distannoxane catalyst at 100 °C under nitrogen atmosphere. The second step was the preparation of poly(urethane‐ester) by polymerizing 4,4′‐methylene‐bis(phenyl isocyanate) (MDI) and prepolymers with various chain lengths in the absence of catalysts. The poly(urethane‐ester) was characterized through an analysis of functional groups (FTIR), thermal properties (differential thermal analysis/TGA), mechanical properties (tensile tester), crystallinity (XRD) and biodegradability. An increased chain length of the prepolymer used in polymerization with MDI leads to an increase in the thermal properties and crystallinity of poly(urethane‐ester). However, the maximum biodegradability in the activated sludge was observed in the poly(urethane‐ester) prepared by polymerizing MDI and prepolymers with a molar VL/DP ratio of 20/1. The amorphous parts of polymers were more easily decomposed by microorganism enzymes than were the crystalline parts after an incubation period of 30 days. Copyright © 2011 Society of Chemical Industry     

Multistep Model of Cervical Cancer: Participation of miRNAs and Coding Genes

Aberrant miRNA expression is well recognized as an important step in the development of cancer. Close to 70 microRNAs (miRNAs) have been implicated in cervical cancer up to now, nevertheless it is unknown if aberrant miRNA expression causes the onset of cervical cancer. One of the best ways to address this issue is through a multistep model of carcinogenesis. In the progression of cervical cancer there are three well-established steps to reach cancer that we used in the model proposed here. The first step of the model comprises the gene changes that occur in normal cells to be transformed into immortal cells (CIN 1), the second comprises immortal cell changes to tumorigenic cells (CIN 2), the third step includes cell changes to increase tumorigenic capacity (CIN 3), and the final step covers tumorigenic changes to carcinogenic cells. Altered miRNAs and their target genes are located in each one of the four steps of the multistep model of carcinogenesis. miRNA expression has shown discrepancies in different works; therefore, in this model we include miRNAs recording similar results in at least two studies. The present model is a useful insight into studying potential prognostic, diagnostic, and therapeutic miRNAs.     

MoS2-Polyaniline Based Flexible Electrochemical Biosensor: Toward pH Monitoring in Human Sweat

Wearable pH sensors for sweat analysis have garnered significant scientific attention for the detection of early signs of many physiological diseases. In this study, a MoS₂-polyaniline (PANI) modified screen-printed carbon electrode (SPCE) is fabricated and used as a sweat biosensor. The exfoliated MoS₂ nanosheets are drop casted over an SPCE and are functionalized by a conducting polymer, polyaniline (PANI) via the electropolymerization technique. The as-fabricated biosensor exhibits high super-Nernstian sensitivity of −70.4 ± 1.7 mV pH⁻¹ in the linear range of pH 4 to 8 of 0.1 m standard phosphate buffer solution (PBS), with outstanding reproducibility. The sensor exhibits excellent selectivity against the common sweat ions including Na⁺, Cl⁻, K⁺, and NH₄⁺ with tremendous long-term stability over 180 min from pH 4 to 6. The enhanced active surface area and better electrical conductivity as a consequence of the synergistic effect between MoS₂ and PANI are correlated with the boosted performance of the as-produced biosensor. The feasibility of the sensor is further examined using an artificial sweat specimen and the successful detection confirms the potential of the biosensor for a real-time noninvasive, skin attachable, and flexible wearable pH sensor.     

Polymer electrolyte membranes composed of an electrospun poly(vinylidene fluoride) fibrous mat in a poly(4‐vinylpyridine) matrix

Newly proposed polymer electrolyte membranes (PEMs) composed of an electrospun poly(vinylidene fluoride) (PVDF) fibrous mat embedded in a poly(4‐vinylpyridine) (P4VP) matrix were successfully fabricated in order to improve the mechanical and dimensional stabilities and ionic conductivity of membranes in lithium rechargeable batteries. Fourier transform infrared spectroscopic analysis showed that as a result of the use of a high voltage during electrospinning the crystalline structure of PVDF changed partially from α‐phase to β‐phase. Energy‐dispersive X‐ray spectroscopy confirmed the existence of crosslinked P4VP in the PVDF fibrous mat. The electrolyte uptakes of PVDF and PVDF/P4VP composite mats were higher than that of PVDF cast film. The tensile properties of PVDF/P4VP composite mat were considerably improved compared to those of the pristine PVDF fibrous mat under both dry and wet (soaked with electrolyte) conditions. In addition, the mechanical and dimensional stabilities of the PVDF/P4VP composite PEM were further enhanced due to crosslinking between the P4VP chains. Furthermore, the PVDF/P4VP composite PEM exhibited an ionic conductivity that was an order of magnitude higher than that of traditional PVDF film. © 2012 Society of Chemical Industry     

Achieving β-phase poly(vinylidene fluoride) from melt cooling: Effect of surface functionalized carbon nanotubes

Poly(vinylidene fluoride) (PVDF) based nanocomposites with different surface-functionalized multi-walled carbon nanotubes (MWCNTs) were prepared by melt mixing in a small scale compounder. With the incorporation of commercial functionalized MWCNTs, the β-phase in PVDF can be directly achieved from melt cooling, as verified by results of Fourier transform infrared spectrum and X-ray diffraction. Interestingly, nanocomposites with amino group functionalized MWCNTs showed the highest percentage of β-phase (17.4%) formation in PVDF, followed by those with hydroxyl groups (11.6%) and unmodified MWCNTs (9.4%). However, the nanocomposites containing MWCNTs with carboxyl groups which were thought to be able to well interact with the dipoles on PVDF chains have the lowest amount of β-phase, i.e. 4.7%. The analysis on the mechanism of the influence of surface functionalization of MWCNTs on the formation of β-phase in PVDF shows that the combined effects of the dispersion of MWCNTs and the nanotube–polymer interactions account for the formation of the β-phase in PVDF.     

重组弓形虫热休克蛋白70不同途径免疫小鼠诱导的小肠黏膜IgA抗体分泌细胞及sIgA抗体的动态变化

目的分析重组弓形虫热休克蛋白70(rTgHSP70)鼻内或皮下免疫小鼠诱导的小肠黏膜IgA抗体分泌细胞(IgA antibody-secreting cells,IgA-ASCs)与小肠冲洗液sIgA抗体的动态变化及二者的相关性,探讨其上调小肠黏膜免疫应答的作用机制。方法 BALB/c小鼠90只,随机均分3组:鼻内组(20μg rTgHSP70/只,滴鼻,免疫2次,间隔2周)、皮下组(80μg rTgHSP70/只,背部皮下注射,免疫2次,间隔2周)、对照组(不免疫)。分别于末次免疫后第1、2、3、4、5、6周,每组取小鼠5只,脱颈椎处死,免疫组化法检测十二指肠、空肠及回肠黏膜IgA-ASCs数量,ELISA法检测小肠冲洗液sIgA水平。结果 IgA-ASCs分布于小肠黏膜的固有层中,且鼻内组小肠黏膜IgA-ASCs数量明显高于皮下组和对照组(P<0.001),鼻内组小肠冲洗液sIgA水平在免后1～4周均处于上升阶段,第4周达到高峰,显著高于皮下组和对照组,差异有统计学意义(P<0.001);鼻内组和皮下组小肠冲洗液sIgA水平与十二指肠、空肠、回肠黏膜固有层IgA-ASCs的数量呈正相关(P<0.05)。结论 rTgHSP70经鼻内或皮下免疫小鼠均可诱导小肠黏膜固有层IgA-ASCs和小肠冲洗液sIgA水平的持续高表达,且二者呈正相关,鼻内免疫上调小肠黏膜免疫的作用优于皮下免疫。     

Morphological and infra-red studies on highly oriented poly(vinylidene fluoride)/poly(methyl methacrylate) blends

Highly oriented melt drawn films of poly(vinylidene fluoride) (PVDF) and blends of poly(vinylidene fluoride) and poly(methyl methacrylate) (PMMA) have been studied by transmission electron microscopy, electron diffraction and infra-red spectroscopy. Infra-red spectra show the second moment of the orientation function for PVDF samples to be greater than 0.94. Using such a sample, the transition dipole directions relative to the chain axis have been calculated. Electron microscopic studies of the PVDF/PMMA blends show a transformation for pure PVDF from a lamellar morphology to a mixture of lamellar and needle-like crystals for the 80/20 blend. The 60/40 blend shows a pure needle-like morphology. The β phase content for this blend is dependent upon the composition and thermal history. An increase in the β phase content is observed with the addition of PMMA. After annealing at 110°C, the 50/50 blend shows a lamellar β phase morphology. A significant increase in the segmental orientation of PVDF is also observed.     

Multi‐Stage Aqueous Two‐Phase Extraction for the Purification of Monoclonal Antibodies

Using monoclonal antibodies in a cell culture harvest as an example for complex biomolecules, a mini‐plant‐scale aqueous two‐phase purification process was studied. The results of this study indicate that antibodies can be concentrated and purified in a single extraction step employing a small phase ratio. Following the extraction step, a multi‐stage wash‐extraction for further purification was investigated. Starting at a test tube‐scale cross‐current wash, the process was advanced towards a continuous counter‐current mixer‐settler and column wash process. It was shown that a test tube cross‐current extraction operation can predict the multi‐stage purity reasonably well. The hydrodynamic process performance for the multi‐stage wash column was evaluated and related to the separation performance.     

Hydrophilic modification of poly(vinylidene fluoride) membrane with poly(vinyl pyrrolidone) via a cross‐linking reaction

A highly hydrophilic hollow fiber poly(vinylidene fluoride) (PVDF) membrane [PVDF‐cl‐poly(vinyl pyrrolidone) (PVP) membrane] was prepared by a cross‐linking reaction with the hydrophilic PVP, which was immobilized firmly on the outer surface and cross‐section of the PVDF hollow fiber membrane via a simple immersion process. The cross‐linking between PVDF and PVP was firstly verified via nuclear magnetic resonance measurement on PVP solution after cross‐linking. The hydrophilic stability of the modified PVDF membrane was evaluated by measuring the pure water flux after different times of immersion and drying. The anti‐fouling properties were estimated by cyclic filtration of protein solution. When the cross‐linking time was as long as 6 hr and the PVP content reached 5 wt %, the pure water flux (J_v) was constant as ～ 600 L m^?2 hr^?1. The hydrophilicity of the PVDF‐cl‐PVP membrane was significantly enhanced and exhibited a good stability. The PVDF‐cl‐PVP membrane showed an excellent anti‐protein‐fouling performance during the cyclic filtration of bovine serum albumin solution. Therefore, a highly hydrophilic and anti‐protein‐fouling PVDF hollow fiber membrane with a long‐term stability can be prepared by a simple and economical cross‐linking process with PVP. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate)/poly(vinyl pyrrolidone) ternary blends

Ternary blends composed of matrix polymer poly(vinylidene fluoride) (PVDF) with different proportions of poly(methyl methacrylate) (PMMA)/poly(vinyl pyrrolidone) (PVP) blends were prepared by melt mixing. The miscibility, crystallization behavior, mechanical properties and hydrophilicity of the ternary blends have been investigated. The high compatibility of PVDF/PMMA/PVP ternary blends is induced by strong interactions between the carbonyl groups of the PMMA/PVP blend and the CF₂ or CH₂ group of PVDF. According to the Fourier transform infrared and wide‐angle X‐ray difffraction analyses, the introduction of PMMA does not change the crystalline state (i.e. α phase) of PVDF. By contrast, the addition of PVP in the blends favors the transformation of the crystalline state of PVDF from non‐polar α to polar β phase. Moreover, the crystallinity of the PVDF/PMMA/PVP ternary blends also decreases compared with neat PVDF. Through mechanical analysis, the elongation at break of the blends significantly increases to more than six times that of neat PVDF. This confirms that the addition of the PMMA/PVP blend enhances the toughness of PVDF. Besides, the hydrophilicity of PVDF is remarkably improved by blending with PMMA/PVP; in particular when the content of PVP reaches 30 wt%, the water contact angle displays its lowest value which decreased from 91.4° to 51.0°. Copyright © 2011 Society of Chemical Industry     

Adhesive properties onto galvanized steel plates of grafted poly(vinylidene fluoride) powders with phosphonated acrylates

Hydrophilic fluoropolymers were obtained by grafting phosphonated monomers onto activated poly(vinylidene fluoride) (PVDF). By using an ozonization technique, dialkylperoxide and hydroperoxide groups were formed onto PVDF which may be decomposed thermally in a subsequent step to initiate graft copolymerization. By using an iodometric titration technique, the effect of ozone oxidation time and temperature on the concentration of peroxides was studied. However, degradation was observed by viscosimetry and FTIR for the hardest ozonization conditions. An effect of the grafting conditions (monomer concentration and monomer end groups) on the degree of grafting was determined and diester‐acrylated phosphonate is grafted at a higher rate than are the homologous acid derivatives. Adhesion of the graft copolymers applied to galvanized steel substrates was studied. The experiments clearly show stronger adhesive properties of PVDF coatings containing phosphonic acid functions than those of the ones containing carboxylic acid functions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 611–620, 1999     

Adhesive and anticorrosive properties of poly(vinylidene fluoride) powders blended with phosphonated copolymers on galvanized steel plates

Fluoropolymers with adhesive and anticorrosive properties were investigated by blending statistical phosphonated copolymers with poly(vinylidene fluoride) (PVDF). In a first part, methacrylic monomers bearing dialkyl phosphonate and phosphonic acid groups were synthesized. Dimethyl(2‐methacryloyloxyethyl)phosphonate was obtained by carrying out a one‐step methacrylation of a commercial phosphonated alcohol. Then, a chemical conversion of the dimethyl phosphonate group to phosphonic acid groups was accomplished by two routes, including on the one hand a trimethylhalosilane and on the other hand an inorganic halide as dealkylation reagents. The resulting monomers were analyzed by nuclear magnetic resonance (NMR) spectroscopy and results were discussed. In a second part, the phosphonated monomers were copolymerized with methyl methacrylate in the presence of 2,2'‐azobis(isobutyronitrile) (AIBN) to give statistical copolymers in high yields. In a third and last part, copolymers were introduced into PVDF as adhesion promoters and anticorrosion inhibitors. Good dry and wet adhesion properties onto galvanized steel plates were obtained with blends containing mainly phosphonic acid groups. Results of corrosion tests show that the phosphonic acid groups maintain some level of adhesion, thereby preventing the spread of corrosion. However, the number of acid groups and their neighbors influence the adhesive and anticorrosive properties of the PVDF coatings. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2277–2287, 2002     

The effect of lanthanum oxide (La2O3) on the structure and crystallization of poly(vinylidene fluoride)

Rare earth polymers, due to their excellent luminescence, fluorescence, laser protective, optical and magnetic properties, have attracted much research attention in recent years. However, little attention has been paid to the effect of rare earths on the structure and crystallization of polymers, which is of important significance in the development of functional polymers. X‐ray diffraction and differential scanning calorimetry were used to investigate the structure and crystallization behavior of a poly(vinylidene fluoride) (PVDF)/lanthanum oxide (La₂O₃) composite. The results showed that the degree of perfection, crystal size, crystallization rate and isothermal crystallization activation energy of PVDF in the composite decreased, compared with pure PVDF. The spherulite nucleation and growth for PVDF and PVDF composite were analyzed in detail using the Lauritzen‐Hoffman equation. The modified Avrami equation and the Mo equation were used to study the non‐isothermal crystallization kinetics. The addition of La₂O₃ did not change the crystal structure and nucleation process for PVDF, but it decreased markedly the crystal growth rate and led to the formation of unstable crystals. This was attributed to the fact that too much La₂O₃ prevented PVDF molecular chains from moving and arranging in an orderly manner into crystals. Copyright © 2010 Society of Chemical Industry     

Nonisothermal crystallization kinetics of poly(vinylidene fluoride) in a poly(vinylidene fluoride)/dibutyl phthalate/di(2‐ethylhexyl)phthalate system via thermally induced phase separation

The nonisothermal crystallization kinetics of poly(vinylidene fluoride) (PVDF) in PVDF/dibutyl phthalate (DBP)/di(2‐ethylhexyl)phthalate (DEHP) blends via thermally induced phase separation were investigated through differential scanning calorimetry measurements. The Ozawa approach failed to describe the crystallization behavior of PVDF in PVDF/DBP/DEHP blends, whereas the modified Avrami equation successfully described the nonisothermal crystallization process of PVDF. Two stages of crystallization were observed in this analysis, including primary crystallization and secondary crystallization. The influence of the cooling rate and DBP ratio in the diluent mixture on the crystallization mechanism and crystal structure was determined by this method. The Mo approach well explained the kinetics of primary crystallization. An analysis of these two methods indicated that the increase in the DBP ratio in the diluent mixture caused a decrease in the crystallization rate at the primary crystallization stage. The activation energy was determined according to the Kissinger method and also decreased with the DBP ratio in the diluent mixture increasing. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008