A novel gas sensor from crystalline polymer-grafted carbon black: responsibility of electric resistance of composite from crystalline polymer-grafted carbon black against solvent vapor

Summary Crystalline polymers, such as poly(ɛ-caprolactone) (PCL), poly(ethylene adipate) (PEA), and polyethylene (PE), were successfully grafted onto carbon black surface by direct condensation of terminal groups of these polymers with carboxyl groups on the surface using N,N'-dicyclohexylcarbodiimide as a condensing agent. The electric resistance of a composite prepared from these crystalline polymer-grafted carbon black drastically increased to 10⁴–10⁵ times of initial resistance in good solvent vapor of grafted polymer and returned to initial resistance when it was transferred into dry air. However, the change of electric resistance of the composite hardly observed in poor solvent vapor. These results suggest that these composite can be applied as a novel gas sensor. Received: 18 February 1999/Accepted: 25 March 1999     

Responsiveness of electric resistance of polymer-grafted carbon black/alumina gel composite against solvent vapor and solute in solution

The carbon black/alumina gel composites were prepared by sol-gel reaction of aluminum isopropoxide in the presence of polymer-grafted carbon black. The electric resistance of the alumina gel composite from polymer-grafted carbon black was very sensitive to vapor of good solvent for grafted polymer on carbon black: the electric resistance of the alumina gel composite suddenly decreased in solvent vapor and returned to initial resistance when it was transferred into dry air. The effect of surface area and particle size of carbon black on the responsiveness was also investigated. In addition, the electric resistance of the alumina gel composite was found to respond to water and methanol in n-hexane and diethyl ether.     

Responsibility of electric resistance of polyethyleneimine-grafted carbon black against alcohol vapor and humidity

Crystalline polyethyleneimine (PEI(C)) was successfully grafted onto carbon black surface by direct condensation of imino groups of PEI with carboxyl groups on the surface using N,N′-dicyclohexylcarbodiimide as a condensing agent. The electric resistance of a composite prepared from PEI(C) and PEI(C)-grafted carbon black drastically increased to 10³ – 10⁴ times of initial resistance in methanol, ethanol, and water vapor. But the change of electric resistance of the composite hardly observed in hexane and toluene vapor. These results suggest the possibility of detection of a slight change of crystalline structure of PEI by the absorption of solvent as a large increase of electric resistance of the composite. Received: 11 April 1997/Revised: 16 June 1997/Accepted: 23 June 1997     

Novel vapor sensor from polymer-grafted carbon black: effects of heat-treatment and γ-ray radiation-treatment on the response of sensor material in cyclohexane vapor

Polyethylene (PE) was grafted onto carbon black surface by γ-ray radiation of the PE-adsorbed carbon black. Vapor sensor composite materials were prepared from the PE-grafted carbon black and PE as a matrix polymer. The effects of heat-treatment and γ-ray radiation-treatment on the response of the electric resistance of the sensor material against cyclohexane vapor were investigated. The heat-treatment of the composite improved the crystallinity of the matrix PE, and thus increased the responsiveness against cyclohexane vapor about five times that of the untreated one. The γ-ray radiation-treatment slightly decreased the responsiveness against cyclohexane vapor, because the γ-ray radiation-treatment induced the crosslinking of PE. On the contrary, the stability and reproducibility of the vapor sensor material remarkably improved. By the heat-treatment followed by the γ-ray radiation-treatment, a novel stable and reproducible sensor material was obtained, which allowed to identify and to quantify certain vapors in air accurately.     

A novel polycaprolactone‐grafted‐carbon black nanocomposite‐based sensor for detecting solvent vapors

A novel vapor sensor is fabricated with polycaprolactone‐grafted‐carbon black (CB‐g‐PCL) as sensing materials. The influence of PCL with different grafting contents and solvents with various solubility and concentrations including benzene, deionized water, epoxy chloropropane (ECP), ethanol, toluene, and tetrahydrofuran on the response of electric resistance was investigated. When compared with mixture of PCL and carbon black, the CB‐g‐PCL‐based sensor shows high sensitivity and good reproducibility. Sensor with moderate content of grafting PCL showed high sensitivity to vapors. The electric resistance of sensor drastically increased in ECP, ethanol, and deionized water with similar solubility with PCL and showed slight increase in benzene, toluene, and tetrahydrofuran with different solubility. The study on the response of electric resistance of CB‐g‐PCL to different vapors confirmed the swelling‐induced sensing mechanism of sensor based on polymer‐grafted‐conductive nanomaterials. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of graft copolymer polyethylene‐ graft‐poly(ethylene oxide) by a new anionic graft‐from polymerization

A series of amphiphilic graft copolymers, PE‐graft‐PEO, containing hydrophobic polyethylene (PE) as the backbone and hydrophilic poly(ethylene oxide) (PEO) as the side‐chain, have been synthesized by a novel route. The graft structure and the molecular weight, as well as the molecular weight distribution of the graft copolymer can easily be controlled. The molecular weight of the side‐chain PEO is proportional to the reaction time and the monomer concentration, which indicates the ‘living’ character of the anionic polymerization of ethylene oxide. The produced copolymers PE‐graft‐PEO were characterized by ¹H NMR and DSC measurements. Copyright © 2004 Society of Chemical Industry     

The functions of crystallizable ethylene‐propylene copolymers in the formation of multiple phase morphology of high impact polypropylene

The functions of crystallizable ethylene‐propylene copolymers in the formation of multiple phase morphology of high impact polypropylene (hiPP) were studied by solvent extraction fractionation, transmission electron microscopy (TEM), selected area electron diffraction (SAED), nuclear magnetic resonance (¹³C‐NMR), and selected reblending of different fractions of hiPP. The results indicate that hiPP contains, in addition to polypropylene (PP) and amorphous ethylene‐propylene random copolymer (EPR) as well as a small amount of polyethylene (PE), a series of crystallizable ethylene‐propylene copolymers. The crystallizable ethylene‐propylene copolymers can be further divided into ethylene‐propylene segmented copolymer (PE‐s‐PP) with a short sequence length of PE and PP segments, and ethylene‐propylene block copolymer (PE‐b‐PP) with a long sequence length of PE and PP blocks. PE‐s‐PP and PE‐b‐PP participate differently in the formation of multilayered core‐shell structure of the dispersed phase in hiPP. PE‐s‐PP (like PE) constructs inner core, PE‐b‐PP forms outer shell, while intermediate layer is resulted from EPR. The main reason of the different functions of the crystallizable ethylene‐propylene copolymers is due to their different compatibility with the PP matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of amphiphilic block copolymer of polyacrylonitrile‐block‐poly(ethylene oxide)

The synthesis of polyacrylonitrile‐block‐poly(ethylene oxide) (PAN‐b‐PEO) diblock copolymers is conducted by sequential initiation and Ce(IV) redox polymerization using amino‐alcohol as the parent compound. In the first step, amino‐alcohol potassium with a protected amine group initiates the polymerization of ethylene oxide (EO) to yield poly(ethylene oxide) (PEO) with an amine end group (PEO‐NH₂), which is used to synthesize a PAN‐b‐PEO diblock copolymer with Ce(IV) that takes place in the redox initiation system. A PAN‐poly(ethylene glycol)‐PAN (PAN‐PEG‐PAN) triblock copolymer is prepared by the same redox system consisting of ceric ions and PEG in an aqueous medium. The structure of the copolymer is characterized in detail by GPC, IR, ¹H‐NMR, DSC, and X‐ray diffraction. The propagation of the PAN chain is dependent on the molecular weight and concentration of the PEO prepolymer. The crystallization of the PAN and PEO block is discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1753–1759, 2003     

A conductive foam: Based on novel poly(styrene‐b‐butadiene‐co‐styrene‐b‐styrene) tri‐block copolymer filled by carbon black

In this article, a conductive foam based on a novel styrene‐based thermoplastic elastomer called poly(styrene‐b‐butadiene‐co‐styrene‐b‐styrene) tri‐block copolymer S(BS)S was prepared and introduced. S(BS)S was particularly designed for chemical foaming with uniform fine cells, which overcame the shortcomings of traditional poly(styrene‐b‐butadiene‐b‐styrene) tri‐block copolymer (SBS). The preparation of conductive foams filled by the carbon black was studied. After the detail investigation of cross‐linking and foaming behaviors using moving die rheometer, the optimal foaming temperature was determined at 180°C with a complex accelerator for foaming agent. Scanning electron microscopy (SEM) images shown that the cell bubbles of conductive foam were around 30–50 µm. The conductivity of foams was tested using a megger and a semiconductor performance tester. SEM images also indicated that the conductivity of foams was mainly affected by the distribution of carbon black in the cell walls. The formation of the network of the carbon black aggregates had a contribution to perfect conductive paths. It also found that the conductivity of foams declined obviously with the foaming agent content increasing. The more foaming agent led to a sharp increasing of the number of cells (from 2.93 × 10⁶ to 6.20 × 10⁷ cells/cm³) and a rapid thinning of the cell walls (from 45.3 to 1.4 µm), resulting in an effective conductive path of the carbon black no forming. The conductive soft foams with the density of 0.48–0.09 g/cm³ and the volume resistivity of 3.1 × 10³?2.5 × 10⁵ Ω cm can be easily prepared in this study. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41644.     

Novel comb‐structured‐polymer‐grafted carbon black by surface‐initiated atom transfer radical polymerization and ring‐opening polymerization

Novel comb‐structured‐polymer‐grafted carbon black (CB) was synthesized with a combination of surface‐initiated atom transfer radical polymerization and ring‐opening polymerization. First, poly(2‐hydroxyethyl methacrylate) (PHEMA) was grafted onto the CB surface by surface‐initiated atom transfer radical polymerization. The prepared CB‐g‐PHEMA contained 35.6–71.8% PHEMA, with the percentage depending on the molar ratio of the reagents and the reaction temperature. Then, with PHEMA in CB‐g‐PHEMA as the macroinitiator, poly(?‐caprolactone) (PCL) was grown from the CB‐g‐PHEMA surface by ring‐opening polymerization in the presence of stannous octoate. CB‐g‐PHEMA and CB‐g‐(PHEMA‐g‐PCL) were characterized with Fourier transform infrared, ¹H‐NMR, thermogravimetric analysis, dynamic light scattering, and transmission electron microscopy. The resultant grafted CB had a shell of PHEMA‐g‐PCL. On the whole, the CB nanoparticles were oriented in dendritic lamellae formed by these shells. This hopefully will result in applications in gas sensor materials and nanoparticle patterns. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influences of the chain structure of PE‐b‐PEG on the properties of PE/PE‐b‐PEG blend membranes prepared by TIPS

In this article, a series of diblock copolymer polyethylene‐b‐ poly(ethylene glycol)s (PE‐b‐PEGs) with various molecular weight of polyethylene segment was blended with linear low‐density PE. The PE/PE‐b‐PEG blend porous membranes with high porosity were obtained by thermally induced phase separation (TIPS) process. The isothermal crystallization kinetics of PE/LP/PE‐b‐PEG blends indicated that the introduction of PE‐b‐PEG could inhibit the growth rate of polyethylene crystals which could increase the pore size and porosity of the membranes. The PE/PE‐b‐PEG blend membranes with PE₁₃₀₀‐b‐PEG₂₂₀₀ showed the largest pore size and porosity due to its crystallization behavior during TIPS. The surface of the membranes became smoother and the morphology of the membranes could be effectively tuned by introducing PE‐b‐PEG. Compared with the PE membrane, the PE/PE‐b‐PEG blend membranes exhibited higher hydrophilicity (the water contact angle decreased from 112° to 84°), water permeability (the permeation flux increased from 80 to 440 L/m² h under 0.1 MPa), rejection performance (completely reject carbon particles in the filtration of carbon ink solution), and fouling resistance (the value of protein adsorption dropped from 0.25 to 0.05 mg/cm²). The hydrophilicity and fouling resistance of PE/PE‐b‐PEG blend membranes increased as the length of PE segment in PE‐b‐PEGs decreased. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46499.     

Highly sensitive toluene vapor sensors using carbon black/amino‐functional copolymer composites

An amino‐functional copolymer [N,N,‐dimethyl‐1,3‐propanediamine (MCD)] developed in our laboratory was blended with carbon black (CB/MCD composite) and its electrical responses to toluene vapor at low concentrations were measured at 30°C. When exposed to 200 ppm of toluene vapor, the CB/MCD sensor responded at S = 0.04 (S was obtained by dividing the relative change in the resistance of the sensor upon exposure to toluene vapor by the baseline resistance), demonstrating its ability to detect toluene vapor at low concentrations. The response was affected by humidity in the atmosphere due to the hydrophilic nature of MCD film; however, the behavior was reproducible before and after exposure of the sensor to the humid atmosphere. In addition, in 10 consecutive sorbing/desorbing cycles, it was confirmed that the changes in the resistance of the CB/MCD sensor were reproducible. These favorable sensing characteristics were attributed to vapor sorption behavior arising from the glassy and loosely crosslinked nature of MCD and explained by the dual‐sorption model. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Investigating nonlinear viscoelastic properties of molten carbon black/poly(ethylene‐co‐butyl acrylate) composites,using fourier transform rheometry and other test techniques

A series of molten carbon black (CB)/poly(ethylene‐co‐butyl acrylate) (EBA) composites were investigated through Fourier transform (FT) rheometry and other techniques. Filler loadings were above the critical percolation value, and consequently, strongly nonlinear viscoelastic properties were observed, with, in addition, an unusual complexity of carbon black effects when compared with other systems, for instance filled elastomers. FT rheometry appears particularly sensitive to such a complexity with typical variations of torque harmonics, as dynamic torsional strain is increased at constant frequency and temperature. How CB particles are distributed in the material appears as the key to understand experimental results. Indeed, in CB–EBA composites, filler particles concentrate in amorphous regions of the polymer, which are also butyl acrylate (BA)‐rich regions. At room temperature, such composites are basically dual‐phase systems: ethylene segments (PE)‐rich crystallites and CB‐rich amorphous BA regions. Solid‐state mechanical properties reflect this morphology. As temperature increases, crystallites melt down allowing a pseudofluid state to be eventually reached but the dual‐phase morphology is essentially kept. It follows that, under increasing (dynamic) strain, such complex dual‐phase molten systems exhibit a response that initially reflects a contribution from PE‐rich regions, easier to deform than CB‐rich amorphous BA regions, before the expected response of the filled BA phase is observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4071–4082, 2006     

Preparation and conductive properties of polycaprolactone‐grafted carbon black nanocomposites

Polycaprolactone‐grafted carbon black (CB‐g‐PCL) nanocomposites were prepared by surface‐initiated ring‐opening polymerization of ε‐caprolactone on the surface of CB. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), atomic force microscope (AFM), X‐ray diffraction (XRD), and polarizing optical microscope (POM) method were employed to characterize the resultant CB‐g‐PCL. The effect of temperature on resistivity of polycaprolactone‐grafted CB (CB‐g‐PCL) nanocomposites was investigated and compared with that of mixture of CB and PCL. It was found that CB‐g‐PCL nanocomposites exhibited positive temperature coefficient (PTC) phenomena between 48 and 51°C, and negative temperature coefficient (NTC) phenomena and between 51 and 54°C. The prepared CB‐g‐PCL nanocomposites have the potential to be temperature‐dependent switch materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystallization behavior of “wet brush” and “dry brush” blends of PS‐b‐PEO‐b‐PS/h‐PEO

The crystallization behavior of the blending system consists of homopolymer poly(ethylene oxide) (h‐PEO) with different molecular weights, and polystyrene‐block‐poly (ethylene oxide)‐block‐polystyrene (PS‐b‐PEO‐b‐PS) triblock copolymer has been investigated by DSC measurements. The crystallization of PEO block (b‐PEO) in block copolymer occurs under much lower temperature than that of the h‐PEO in the bulk (ΔT > 65 °C), which is attributed to the homogeneous nucleation crystallization behavior of the b‐PEO microdomains. In both the “dry‐brush” and the “wet brush” blending systems, the homogeneous nucleation crystallization temperature of PS‐b‐PEO‐b‐PS/h‐PEO blends increases due to the increase of the domain size. The heterogeneous nucleation crystallization temperatures of h‐PEO in the wet brush blending systems are higher than that of the corresponding h‐PEO in the bulk. At the same time, the heterogeneous nucleation crystallization temperature of b‐PEO10000 decreases from 43°C to 30°C and 40°C in the h‐PEO600 and h‐PEO2000 blending systems, respectively, because of the stretching of the PEO chains in the wet brush. However, this kind of phenomenon does not happen in the dry brush blending systems. The self‐seeding procedure was used to further ascertain the nucleation mechanism in the crystallization process. As a result, the self‐seeding domains have been confirmed, and the difference between the dry brush and wet brush systems has been observed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Poly(ethylene‐graft‐ethylene oxide) (PE‐PEO) and poly(ethylene‐co‐acrylic acid) (PEAA) as compatibilizers in blends of LDPE and polyamide‐6

In a blend of two immiscible polymers a controlled morphology can be obtained by adding a block or graft copolymer as compatibilizer. In the present work blends of low‐density polyethylene (PE) and polyamide‐6 (PA‐6) were prepared by melt mixing the polymers in a co‐rotating, intermeshing twin‐screw extruder. Poly(ethylene‐graft‐polyethylene oxide) (PE‐PEO), synthesized from poly(ethylene‐co‐acrylic acid) (PEAA) (backbone) and poly(ethylene oxide) monomethyl ether (MPEO) (grafts), was added as compatibilizer. As a comparison, the unmodified backbone polymer, PEAA, was used. The morphology of the blends was studied by scanning electron microscopy (SEM). Melting and crystallization behavior of the blends was investigated by differential scanning calorimetry (DSC) and mechanical properties by tensile testing. The compatibilizing mechanisms were different for the two copolymers, and generated two different blend morphologies. Addition of PE‐PEO gave a material with small, well‐dispersed PA‐spheres having good adhesion to the PE matrix, whereas PEAA generated a morphology characterized by small PA‐spheres agglomerated to larger structures. Both compatibilized PE/PA blends had much improved mechanical properties compared with the uncompatibilized blend, with elongation at break (ε_b) increasing up to 200%. Addition of compatibilizer to the PE/PA blends stabilized the morphology towards coalescence and significantly reduced the size of the dispersed phase domains, from an average diameter of 20 μm in the unmodified PE/PA blend to approximately 1 μm in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2416–2424, 2000     

Synthesis and characterization of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers by atom‐transfer radical polymerization

Well‐defined polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐PS triblock copolymers were synthesized by atom‐transfer radical polymerization (ATRP), using C—X‐end‐group PEO as macroinitiators. The triblock copolymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The experimental results showed that the polymerization was controlled/living. It was found that when the number‐average molecular weight of the macroinititors increased from 2000 to 10,000, the molecular weight distribution of the triblock copolymers decreased roughly from 1.49 to 1.07 and the rate of polymerization became much slower. The possible polymerization mechanism is discussed. According to the Cu content measured with atomic absorption spectrometry, the removal of catalysts, with CHCl₃ as the solvent and kaolin as the in situ absorption agent, was effective. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2882–2888, 2000     

Synthesis and characterization of thermo‐ and pH‐sensitive block copolymers bearing a biotin group at the poly(ethylene oxide) chain end

A poly(ethylene oxide)‐block‐poly(dimethylamino ethyl methacrylate) block copolymer (PEO‐b‐PDMAEMA) bearing an amino moiety at the PEO chain end was synthesized by a one‐pot sequential oxyanionic polymerization of ethylene oxide (EO) and dimethylamino ethyl methacrylate (DMAEMA), followed by a coupling reaction between its PEO amino and a biotin derivative. The polymers were charac terized with ¹H NMR spectroscopy and gel permeation chromatography. Activated biotin, biotin‐NHS (N‐hydroxysuccinimide), was used to synthesize biotin‐PEO‐PDMAEMA. In aqueous media, the solubility of the copolymer was temperature‐ and pH‐sensitive. The particle size of the micelle formed from functionalized block copolymers was determined by dynamic light scattering. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3552–3558, 2006     

Synthesis and characterization of novel hybrid polyoxazoline‐grafted multiwalled carbon nanotubes

The novel hybrid polyoxazoline‐grafted multiwalled carbon nanotubes (POZO‐grafted MWNTs) were synthesized by the reaction of partially hydrolyzed polyoxazolines (Hydrolyzed‐POZO) and MWNTs having carboxylic acid groups (MWNT‐COOH) in the presence of DCC as a condensing agent. Hydrolyzed‐POZO (degree of hydrolysis, 20.2 mol % by ¹H‐NMR) were produced from the hydrolysis of polyoxazolines in an aqueous NaOH solution at reflux for 72 h. MWNT‐COOH were prepared by acid treatment of pristine MWNTs. The composition, structure, thermal property, and surface morphology of the novel hybrid POZO‐grafted MWNTs were fully characterized by FT‐IR, Raman, ¹H‐NMR, DSC, TGA, SEM, and TEM. The obtained POZO‐grafted MWNTs are well soluble in various organic solvents and water. It was observed that the glass transition temperature (T_g) of POZO‐grafted MWNTs was lower than that of Hydrolyzed‐POZO due to the absence of hydrogen bonding interactions between Hydrolyzed‐POZO itself caused by the incorporation with MWNTs. It was also found that Hydrolyzed‐POZO was homogeneously attached to the surfaces of MWNTs through the “grafting‐to” method. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010