Fluorescence turn‐on chemical sensor based on water‐soluble conjugated polymer/single‐walled carbon nanotube composite

A chemical sensor for methyl viologen (MV²⁺), based on a water‐soluble conjugated polymer/single‐walled carbon‐nanotube (SWNT) composite, was fabricated. Water‐soluble poly(m‐phenylene ethynylene) with sulfonic acid side‐chain groups (mPPE‐SO₃) was synthesized via a Pd‐catalyzed Sonogashira coupling reaction and used to prepare a highly stable mPPE‐SO₃/SWNT composite with strong π–π interactions in water. The relationship between the optical properties and sensing capability of the mPPE‐SO₃/SWNT composite in aqueous solution was investigated. The addition of MV²⁺ enhanced the fluorescence intensity of the mPPE‐SO₃/SWNT composite by inducing a conformational change of the polymer from a helical to a random‐coil structure. The water‐soluble mPPE‐SO₃/SWNT composite enabled highly sensitive fluorescence detection of MV²⁺ in aqueous solutions with no precipitation resulting from reaggregation of the SWNTs. This mPPE‐SO₃/SWNT composite sensor system is therefore an effective turn‐on chemical sensor for MV²⁺. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43301.     

Preparation and properties of carbon nanotube/binary‐polymer composites with a double‐segregated structure

A carbon nanotube (CNT)/poly(methyl methacrylate) (PMMA)/ultrahigh molecular weight polyethylene (UHMWPE) composite containing a double‐segregated structure was formalized by means of a facile mechanical mixing technology. In the composite, the CNTs were decorated on the surfaces of PMMA granules, and the CNTs decorated granules formed the continuous segregated conducting layers at the interfaces between UHMWPE particles. Morphology observations confirmed the formation of a specific double‐segregated CNT conductive network, resulting in an ultralow percolation threshold of ～0.2 wt %. The double‐segregated composite containing only 0.8 wt % CNT loading exhibited a high electrical conductivity of ～0.2 S m^?1 and efficient electromagnetic shielding effectiveness of ～19.6 dB, respectively. The thermal conductivity, temperature‐resistivity behaviors, and mechanical properties of the double‐segregated composites were also studied. This work provided a novel conductive network structure to attain a high‐performance conducting polymer composite at low filler loadings. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39789.     

Influence of processing condition and carbon nanotube on mechanical properties of injection molded multi‐walled carbon nanotube/poly(methyl methacrylate) nanocomposites

In this work, multi‐walled carbon nanotubes (MWCNT) and poly(methyl methacrylate) (PMMA) pellets were compounded via corotating twin‐screw extruder. The produced MWCNT/PMMA nanocomposite pellets were injection molded. The effect of MWCNT concentration, injection melt temperature and holding pressure on mechanical properties of the nanocomposites were investigated. To examine the mechanical properties of the MWCNT/PMMA nanocomposites, tensile test, charpy impact test, and Rockwell hardness are considered as the outputs. Design of experiments (DoE) is done by full factorial method. The morphology of the nanocomposites was performed using scanning electron microscopy (SEM). The results revealed when MWCNT concentration are increased from 0 to 1.5 wt %, tensile strength and elongation at break were reduced about 30 and 40%, respectively, but a slight increase in hardness was observed. In addition, highest impact strength belongs to the nanocomposite with 1 wt % MWCNT. This study also shows that processing condition significantly influence on mechanical behavior of the injection molded nanocomposite. In maximum holding pressure (100 bar), the nanocomposites show highest tensile strength, elongation, impact strength and hardness. According to findings, melt temperature has a trifle effect on elongation, but it has a remarkable influence on tensile strength. In the case of impact strength, higher melt temperature is favorable. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43738.     

Effect of glass fiber on the electrical resistivities of polyoxymethylene/maleic anhydride‐grafted polyethylene/multiwalled carbon nanotube composites

The effect of glass fiber (GF) on the electrical resistivities of polyoxymethylene (POM)/maleic anhydride‐grafted polyethylene (MAPE)/multiwalled carbon nanotube (MWCNT) composites is investigated. The POM/MAPE/MWCNT composites at a MWCNT loading of 0.75% are nonconductive because most of MWCNTs are isolated in the MAPE islands, and their electrical resistivities decrease significantly after the addition of GF because of the formation of MAPE‐coated GF structure, which facilitates the formation of conductive paths and was confirmed by field emission scanning electron microscopy (FESEM). The formation of MAPE‐coated GF structure is attributed to the interaction between GF and MAPE during melt compounding, as contrasted by the uncoated GF using high‐density polyethylene (HDPE) instead of MAPE. Nonconductive POM/5–20% MAPE/0.75% MWCNT composites become conductive upon the addition of 20% GF. This preparation method for conductive materials can be generalized to POM/5–20% maleic anhydride‐grafted polypropylene (MAPP)/0.75% MWCNT composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41794.     

Electrical conductivity and tensile properties of block‐copolymer‐wrapped single‐walled carbon nanotube/poly(methyl methacrylate) composites

Poly(methyl methacrylate) (PMMA) composites containing raw or purified single‐walled carbon nanotubes (SWCNTs) are prepared by in situ polymerization and solution processing. The SWCNTs are purified by centrifugation in a Pluronic surfactant, which consists of polyethyleneoxide and polypropyleneoxide blocks. Both the effects of SWCNT purity and non‐covalent functionalization with Pluronic are evaluated. Electrical conductivity of PMMA increases by 7 orders of magnitude upon the integration of raw or purified SWCNTs. The best electrical properties are measured for composites made of purified SWCNTs and prepared by in situ polymerization. Strains at fracture of the SWCNT/PMMA composites are nearly identical to those of the neat matrix. A certain decrease in the work to fracture is measured, particularly for composites containing purified SWCNTs (?31.6%). Fractography and Raman maps indicate that SWCNT dispersion in the PMMA matrix improves upon the direct addition of Pluronic, while dispersion becomes more difficult in the case of purified SWCNTs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41547.     

Electrical,mechanical, and crystallization properties of ethylene‐tetrafluoroethylene copolymer/multiwalled carbon nanotube composites

Multiwalled carbon nanotubes (MWCNTs) were melt‐mixed in a conical twin‐screw extruder with a random copolymer of ethylene and tetrafluoroethylene. Surprisingly, the electrical percolation threshold of the resultant composites was quite low; ～0.9 wt %. In fact, this value is as low or lower than the value for most MWCNT/semicrystalline polymer composites made with roughly equivalent aspect ratio tubes mixed in a similar manner, for example, melt mixing. This low percolation threshold, suggestive of good dispersion, occurred even though the polymer surface energy is quite low which should make tubes more difficult to disperse. Dynamic mechanical measurements confirmed the rather low percolation threshold. The effect of nanotubes on crystallization kinetics was quite small; suggesting perhaps that a lack of nucleation which in turn reduces/eliminates an insulating crystalline polymer layer around the nanotubes might explain the low percolation threshold. Finally, the modulus increased with the addition of nanotubes and the strain at break decreased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41052.     

Tailored dielectric and mechanical properties of noncovalently functionalized carbon nanotube/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) nanocomposites

The preparation of high‐dielectric poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) (SEBS) composites containing functionalized single‐walled carbon nanotubes (f‐SWCNTs) noncovalently appended with dibutyltindilaurate are reported herein. Transmission electron microscopy and X‐ray photoelectron and Raman spectroscopy confirmed the noncovalent functionalization of the SWCNTs. The SEBS‐f‐SWCNT composites exhibited enhanced mechanical properties as well as a stable and high dielectric constant of approximately 1000 at 1 Hz with rather low dielectric loss at 2 wt% filler content. The significantly enhanced dielectric property originates from the noncovalent functionalization of the SWCNTs that ensures good dispersion of the f‐SWCNTs in the polymer matrix. The f‐SWCNTs also acted as a reinforcing filler, thereby enhancing the mechanical properties of the composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A comparative study on effect of aromatic polyimide chain conformation on reinforcement of carbon nanotube/polyimide nanocomposites

Two kinds of polyimides (PIs) were selected as matrices for multiwalled carbon nanotubes (CNTs)‐based nanocomposites. The two PIs were initially synthesized through reactions of a same benzoxazole‐containing diamine with two different dianhydrids. A linear PI was formed from the ether bond‐containing dianhydride, while a nonlinear PI was formed from the ? C(CF3)_2? groups containing dianhydride. Optimized dispersion of nanotubes in both kinds of PIs was found to be at a concentration with 0.5 wt % COOH‐CNT, where great enhancement was achieved for both PIs. It was also found that introducing nanotubes into PI matrices aroused more significant increase of Young's modulus and break stress in linear PI than that in nonlinear PI. To determine the key parameters involved in design of PIs for maximum reinforcement efficiency using CNT as the nanofiller, the nanoscopic dispersion state of the nanotubes in diamine solution and their reaction were investigated via morphological and spectroscopic studies. The interfacial interactions between nanotubes and two PI chains were characterized by FT‐IR and Raman spectroscopy. The fracture surface characteristics of two series of CNT/PI nanocomposites were further investigated using SEM. Our findings show that the diamine plays a double role for the in‐situ polymerization, a dispersant to disentangle the CNT agglomerates and a monomer for PI synthesis with dianhydrides. It was also found that geometry and flexibility of PI chains are crucial to determine the interfacial interactions between nanotubes and PI chains. For elucidating the different interfacial characteristics of the two PIs on the surface of CNT, we proposed a model for preferred conformation adopted by a single PI chain on a single CNT. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40479.     

Mass production of carbon nanotube‐reinforced polyacrylonitrile fine composite fibers

A facile and large‐scale production method of polyacrylonitrile (PAN) fibers and carboxyl functionalized carbon nanotube reinforced PAN composite fibers was demonstrated by the use of Forcespinning® technology. The developed polymeric fibers and carbon nanotube‐reinforced composite fibers were subsequently carbonized to obtain carbon fiber systems. Analysis of the fiber diameter, homogeneity, alignment of carbon nanotube and bead formation was conducted with scanning electron microscopy. Thermogravimetric analysis, electrical, and mechanical characterization were also conducted. Raman and FTIR analyses of the developed fiber systems indicate interactions between carbon nanotubes and the carbonized PAN fibers through π–π stacking. The carbonized carbon nanotube‐reinforced PAN composite fibers possess promising applications in energy storage applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40302.     

Structure,mechanical, and electrical properties of high‐density polyethylene/multi‐walled carbon nanotube composites processed by compression molding and blown film extrusion

The structure and properties of melt mixed high‐density polyethylene/multi‐walled carbon nanotube (HDPE/MWCNT) composites processed by compression molding and blown film extrusion were investigated to assess the influence of processing route on properties. The addition of MWCNTs leads to a more elastic response during deformations that result in a more uniform thickness distribution in the blown films. Blown film composites exhibit better mechanical properties due to the enhanced orientation and disentanglement of MWCNTs. At a blow up ratio (BUR) of 3 the breaking strength and elongation in the machine direction of the film with 4 wt % MWCNTs are 239% and 1054% higher than those of compression molded (CM) samples. Resistivity of the composite films increases significantly with increasing BURs due to the destruction of conductive pathways. These pathways can be recovered partially using an appropriate annealing process. At 8 wt % MWCNTs, there is a sufficient density of nanotubes to maintain a robust network even at high BURs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42665.     

Effect of crosslink density on thermal conductivity of epoxy/carbon nanotube nanocomposites

The effect of the polymeric crosslink density on the thermal conductivity of an epoxy nanocomposite was investigated by adding two different diamine‐functionalized multiwalled carbon nanotubes (diamine‐MWNTs) to the epoxy resin as co‐curing agents and conducting fillers. Tetramethylenediamine (TMDA)‐MWNTs resulted in an epoxy nanocomposite with a higher crosslink density than octamethylenediamine (OMDA)‐MWNTs. Interestingly, epoxy/TMDA‐MWNT nanocomposites under 1.5 wt % nanotube concentration, showed a higher thermal conductivity than an epoxy/OMDA‐MWNT nanocomposite with the same concentration of nanotubes. In contrast, for higher diamine‐MWNT concentrations (over 2.0 wt %), the thermal conductivity of the epoxy/OMDA‐MWNT nanocomposite was higher than that with TMDA‐MWNTs. We observed that for low MWNT concentrations, where a percolating network was not formed, a high crosslink density enhanced the thermal conductivity via phonon transport. However, for high MWNT concentrations, a high crosslink density hinders the formation of a percolating network and lowers the thermal conductivity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44253.     

Improvement of electrical conductivity with phase‐separation in polyolefin/multiwall carbon nanotube/polyethylene oxide composites

Electrical conductivity developments of polypropylene (PP)/multiwall carbon nanotube (MWNT) and polybutene (PB)/MWNT composites were carried out with polyethylene oxide (PEO) phase‐separation behavior for the polymeric materials. The low conductivity (8.47 × 10^?8 S cm^?1) of PP(98%)/MWNT (2%) was drastically increased up to 1.56 × 10^?3 S cm^?1 by only 2% PEO(96%)/MWNT(4%) loading. The drastic improvement originated from the formation of an electrical connector structure with the PEO/MWNT domain. The PB(93%)/MWNT(7%) conductivity was also improved by the PEO(92%)/MWNT(8%) loading although the conductivity improvement effect was lower than that of the PP/MWNT. The Raman spectra showed that the MWNT dispersity in the PB was poorer than that in the PP, resulting in the formation of a PEO/MWNT connector structure only at higher loading. In addition, a PEO/carbon black composite was able to produce the connector structure for the PP/MWNT as well as the PEO/MWNT. These results indicated that the highly conductive composites could be produced with smaller MWNT amounts. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Recent advances in bio‐sourced polymeric carbohydrate/nanotube composites

Nanotubes (NTs), especially carbon nanotubes (CNTs), have attracted much attention in recent years because of their large specific surface area, and their outstanding mechanical, thermal, and electrical properties. In this review we emphasize the development of fascinating properties of polymeric carbohydrate/CNT composites, particularly in terms of their mechanical and conductivity properties and potential applications. Many methods used to modify CNTs during preparation of polymeric carbohydrate/CNT composites are presented. Moreover, we also discuss the enhanced mechanical and electrical effectiveness when hybrid CNTs or halloysite nanotubes were incorporated into different carbohydrate polymer matrices. Finally, we give a future outlook for the development of polymeric carbohydrate/CNT composites as potential alternative materials for various applications including sensors, electroactive paper, electrodes, sorbents for environmental remediation, packaging film, specialty textile, and biomedical devices. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40359.     

A facile synthesis of a novel three‐phase nanocomposite: Single‐wall carbon nanotube/silver nanohybrid fibers embedded in sulfonated polyaniline

A three‐phase water‐soluble nanocomposite of single wall carbon nanotube/silver nanoparticle hybrid fibers embedded in sulfonated polyaniline has been synthesized by a simple chemical solution mixing process. The nanocomposite has been characterized by high resolution electron microscopy, X‐ray diffractometry, FTIR spectroscopy, Raman spectroscopy, and thermogravimetric analysis. Optical and electrical characteristics of the nanocomposite have been determined by UV–vis absorption spectroscopy, photoluminescence spectroscopy, and four‐probe electrical conductivity measurement. A surface plasmon absorption band obtained around 460 nm indicates the presence of silver nanoparticles in the composite. The optical band gap calculation for sulfonated polyaniline vis‐a‐vis the nanocomposite supported the conductivity measurement. Over 1300 times increase in DC electrical conductivity has been observed for the three‐phase nanocomposite, with a filler loading of 20 wt %, at 306 K. This observation could be explained by Mott's variable range hopping model considering a three‐dimensional conduction. Such a nanocomposite has immense potential for use as a cathode material in lithium‐ion batteries and supercapacitors. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41692.     

Effect of carbon nanotube dispersion on the complex permittivity and absorption of nanocomposites in 2–18 GHz ranges

The effect of dispersion processes on complex permittivity and microwave absorption in 2?18 GHz ranges is presented for nanocomposites loaded with different amounts of carbon nanotubes (CNTs) ranging from 1 to 5 wt %. The ultrasonic sonication (US) method and the three‐roll mill (TRM) method were performed for the manufacturing of the CNT/epoxy absorbers with different dispersing levels. Microscopic observations revealed that the CNT agglomerates were reduced after the TRM process, and individual CNTs were uniformly dispersed in the epoxy resin. For the same weight content of CNT fillers, the percentage increase of between US and TRM samples varies from 35.5% to 101.7% while the corresponding increment of (dielectric loss) varies from 79.6% to 248.8%. A minimum reflection loss for the US sample with 2 wt % CNTs is only ?7.8 dB at 11.3 GHz while the corresponding TRM sample is greatly improved to reach ?37.4 dB at 7.76 GHz for the same matching thickness of 3 mm. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40963.     

Understanding the effects of nanocarbons on flexible polymer chain orientation and crystallization: Polyethylene/carbon nanochip hybrid fibrillar crystal growth

Polyethylene (PE)/carbon nanochip fibers (CNCF) fibrillar crystals were grown under shear flow. The fibrillar crystals ranged from 25 to 200 nm in diameter and bundled to form PE/CNCF macro‐fibers. The PE/CNCF fibers were further processed by hot‐drawing near the PE melting temperature. On the basis of small‐angle X‐ray analysis, it was found that during drawing the presence of CNCF led to continuous extended‐chain PE crystal growth. DSC melting peaks associated with transformation of the orthorhombic to a hexagonal lattice phase in the PE crystal structure (i.e., increased ordering and extension of the polymer chain along the fiber axis) was also observed for drawn hybrid PE/CNCF fibrillar crystals. The orientation factor for the extended‐chain (i.e., shish) crystals in the hybrid as compared to the control fibers improved from 0.88 to 0.93. This work shows the direct evidence that these nanocarbon fillers can promote extended‐chain polymer crystal growth under shear. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40763.     

Advanced ultra‐high molecular weight polyethylene/antioxidant‐functionalized carbon nanotubes nanocomposites with improved thermo‐oxidative resistance

Multiwalled carbon nanotubes (CNTs) functionalized with hindered phenol moieties are dispersed in ultra‐high molecular weight polyethylene (UHMWPE), and the stabilizing action of the antioxidant (AO) functionalized CNTs (AO‐f‐CNTs) is studied through a combination of rheological and spectroscopic (FT‐IR) analyses. The effectiveness of two alternative compounding methods, namely hot compaction (HC) and melt mixing (MM), is compared. The combination of high temperature and mechanical stress experienced during MM brings about noticeable degradation phenomena of the matrix already in the course of the compounding step. Differently, the milder conditions of the HC process preserve the stability of the polymer, making this method preferable when dealing with highly viscous matrices. In addition, HC guarantees a better CNT dispersion, allowing for the maximization of the stabilizing action of the AO grafted on the nanotubes. As a result, the HC samples exhibit improved thermo‐oxidative resistance despite the very low amount of AO grafted onto the CNTs. Besides demonstrating the effectiveness of our AO‐f‐CNTs as stabilizers for polymer matrices, our results prove that CNTs can serve as a support on which grafting specific functional molecules to be dispersed in a host polymer matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42420.     

Conducting epoxy networks modified with non‐covalently functionalized multi‐walled carbon nanotube with imidazolium‐based ionic liquid

Multi‐walled carbon nanotube (MWCNT) was non‐covalently functionalized with room‐temperature ionic liquid (IL), 1‐butyl‐3‐methyl‐imidazolium tetrafluoroborate and blended with epoxy pre‐polymer (ER) with the assistance of ultrasonication in the presence of acetone as a diluting medium. The ability of IL in improving the dispersion of MWCNT in epoxy pre‐polymer was evidenced by transmission optical microscopy. The corresponding epoxy/MWCNT networks cured with anhydride displayed an increase of the electrical conductivity of around three orders of magnitude with the addition of IL in a proportion of MWCNT/IL = 1:5 mass ratio. The effect of IL on dynamic mechanical properties and thermal conductivity was also evaluated. The improved thermal and electrical properties was attributed to the better dispersion of MWCNT within the epoxy matrix by IL, evidenced by transmission electron microscopy of the ER/MWCNT networks cured with anhydride. Raman spectroscopy was also used to confirm the interaction between MWCNT and IL. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43976.     

Preparation of high‐k composites with low dielectric loss based on the double‐layer coaxial structure of inorganic/polymer

This study presents a novel and simple modification of cladding multiwalled carbon nanotubes (MWCNTs) using organic polymer and inorganic nanoparticles to synthesize a product, which has a double‐cladding coaxial structure and can be applied as filler in the dielectric field. The first layer of MWCNTs was coated with polyaniline (PANI) through the oxidation–reduction reaction mechanism using Ce(NH₄)₂(NO₃)₆ as oxidizing agent and metal precursor of cerium oxide. Cerium ions on the second cladding layer of MWCNTs were directly deposited from the solution to the surface of the PANI layer forming the double‐cladding hybrid (CeO₂/PANI@MWCNTs). The external inorganic layer provides an insulating shell, which can prevent the contact between the conductive particles and hinder the migration of electrons between the MWCNTs. The intermediate layer of PANI provides the bonding between CeO₂ and the conductive core of MWCNTs, which also shows lower conductivity than carbon nanotubes. The CeO₂/PANI@MWCNTs were compounded with epoxy (EP) resin and formed a dielectric material with the advantage of reducing dielectric loss while ensuring high dielectric constant. The dielectric constant of the coated MWCNTs/EP composites was 194.90 at 10³ Hz with the content of fillers reaching 30 wt %, which is 28 times that of the pure EP. Accordingly, the dielectric loss of 30 wt % coated MWCNTs/EP composites was only 0.09 at 10³ Hz, which is only 2.25 times that of the pure EP. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46299.     

Fabrication of chitosan/polyvinyl alcohol/amine modified carbon nanotube composite films for rapid chromate removal

Composite adsorbent films with amine and hydroxyl functionalities were synthesized from chitosan (CS), polyvinyl alcohol (PVA), and amine-modified carbon nanotubes (a-MWCNT) by solvent casting method. Weight proportions of CS to PVA and weight percent of a-MWCNT were optimized to achieve highest chromate removal capacity. Structural characteristics of the composites were investigated using scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and thermal gravimetric analysis. Accordingly, incorporation of a-MWCNT to CS/PVA structure resulted in the generation of nanochannels, which enhanced adsorption capacity. Moreover, the composite comprising 0.4% wt. a-MWCNT provided over 99% of Cr (VI) removal from 50 mg L⁻¹ Cr (VI) solution within five minutes of contact time. Redlich–Peterson and Radke–Prausnitz isotherm models provided the highest conformity to adsorption data. Maximum chromate sorption capacity of CS/PVA/a-MWCNT composite film was determined as 134.2 mg g⁻¹ being 172% higher than that of CS/PVA. Regeneration was best achieved in 1.0 M NaOH and the composite was shown to retain at least 70% of its original capacity after five consecutive adsorption–desorption cycles.