Molecular Structure of the Interphase Formed by Plasma-Polymerized Acetylene Films and Steel Substrates

The molecular structure of the interphase between plasma-polymerized acetylene films and steel substrates was determined using in situ reflection-absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). Plasma-polymerized acetylene films were deposited onto polished steel substrates using argon as a carrier gas and inductively coupled, radio frequency (RF)-powered plasma reactors that were interfaced directly to the XPS and Fourier transform infrared (FTIR) spectrometers. RAIR showed that the plasma polymerized films contained large numbers of methyl and methylene groups but only a small number of mono substituted acetylene groups, indicating that there was substantial rearrangement of the monomer molecules during plasma polymerization. Bands were observed near 1020 and 855 cm^-1 in the RAIR spectra that were attributed to skeletal stretching vibrations in C-C-O-Fe groups, indicating that the plasma-polymerized films interacted with the substrate through formation of alkoxide bonds. Another band was observed near 1565 cm^-1 and attributed to carboxylate groups in the interphase between the films and the oxidized surface of the substrate. Results obtained from XPS showed that the surface of the iron substrate consisted mostly of a mixture of Fe₂O₃ and FeOOH and that iron was mostly present in the Fe(III) oxidation state. However, during plasma polymerization of acetylene, there was a tendency for the concentration of FeOOH groups to decrease and for the concentration of Fe(II) to increase, due to the reducing nature of argon/acetylene plasmas. Results from XPS also confirmed the formation of alkoxide and carboxylate groups in the interphase during plasma polymerization of acetylene.     

Surface modification of ilmenite by a novel surfactant dodecyliminodimethylenediphosphoinc acid and its sequent influence on ilmenite floatability

ABSTRACT

In the study, a novel compound of dodecyliminodimethylenediphosphoinc acid was synthesized, and its adsorption mechanism onto ilmenite surface was investigated by zeta potential, Fourier transform infrared (FTIR) and X-ray photoelectron spectroscop (XPS) measurements. The zeta potential measurement results indicated that dodecyliminodimethylenediphosphoinc acid (DDDA) could adsorb onto ilmenite surface, and the optimum pH range for adsorption was 4–8 (similar to the flotation behavior). The FTIR analyses further confirmed that DDDA chemisorbed onto ilmenite surface and formed metal–DDDA complex, rendering the hydrophobic media for flotation. The XPS results provided strong evidences that DDDA species chemisorbed onto ilmenite surface and reacted with Fe ions rather than Ti ions.     

Surface microencapsulated ammonium polyphosphate with beta‐cyclodextrin and its application in wood‐flour/polypropylene composites

In order to improve the hydrophilicity of ammonium polyphosphate (APP), as well as its compatibility with composite matrix, in this research, beta‐cyclodextrin (β‐CD) was crosslinked by polydiphenylmethane diisocyanate (PMDI) and used as clothing to prepare microencapsulated APP (MCAPP) via polymerization in situ . Then, APP and MCAPP were mixed with wood‐flour and polypropylene to manufacture wood‐flour/polypropylene composites (WPCs) by hot pressing. Both APP and MCAPP were characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), water solubility tests, and water contact angle (WCA) tests. Limiting oxygen index (LOI) and cone calorimetry tests were used to investigate the flame retardancy of WPCs. Moreover, laser Raman spectroscopy and real‐time FTIR (RT‐FTIR) were used to explore the flame retardant mechanism. Results indicated that APP was successfully coated by the crosslinked β‐CD. MCAPP showed lower water solubility and better surface hydrophobicity, and WPC/MCAPP performed better flame retardnacy and mechanical properties. POLYM. COMPOS., 38:2312–2320, 2017. © 2015 Society of Plastics Engineers     

Hyperbranched Polyethylenimine Modified Waste Fiberboard Activated Carbon for Enhanced Adsorption of Hexavalent Chromium

The objective of this work is to prepare a hyperbranched polyethylenimine (HBPEI) grafted activated carbon obtained from waste fiberboard for effectively removing Cr(VI) from aqueous solution. The waste fiberboard activated carbon (WFAC) was modified by HBPEI and cross-linked with glutaraldehyde (GA). The optimal modified conditions were as follows: HBPEI molecular weight 10,000 g/mol, HBPEI/WFAC (w/w) 0.5, GA concentration 0.25%, reaction time 60 min. Both pristine WFAC and HBPEI–WFAC were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET), Scanning electronic microscopy (SEM), and Roman spectra. XPS data showed the obvious increase in nitrogen (from 0.72% to 6.65%) after modification. The results of FTIR and XPS suggested that HBPEI was chemically bonded onto the WFAC by the glutaraldehyde (GA) between the amine groups of WFAC and that of HBPEI. HBPEI was also probably grafted onto WFAC through the intermolecular interaction between the carboxylate groups of WFAC and the amine groups of HBPEI. However, the BET surface area of modified WFAC declined slightly (about 200 m²/g). The I_D/I_G of modified WFAC decreased from 0.92 to 0.82, which indicated that the modification process had no significant effect on the graphitization of activated carbon. The adsorption property onto HBPEI–WFAC and the factors containing contact time, pH value, and Cr(VI) concentration were also investigated. Analysis of the Cr(VI) adsorption data was well simulated by the pseudo-second-order kinetic model and Langmuir adsorption isotherm model, and maximum Cr(VI) uptake of HBPEI–WFAC was 500 mg/g.     

Structure and composition of the surface of urethane/acrylic composite latex films

Polyurethane dispersions were prepared and urethane/acrylic composite latices were synthesized with polyurethane dispersions as the seed, and core‐shell emulsion polymerization. Fourier‐transform infrared spectroscopy coupled with attenuated total reflectance (FTIR‐ATR) analyses showed that the films obtained from the composite latices were rich in polyurethane component or segments at air‐facing and substrate‐facing surfaces, in comparison with their average composition. Moreover, the substrate‐facing surface contained even more polyurethane component or segments than the air‐facing surface. X‐ray photoelectron spectroscopy (XPS) detection also indicated that the polyurethane component or segments preferentially migrated to the surface layer of the films from the bulk, and that the films from blend latices displayed more polyurethane component or segments near the surface layer. Both FTIR‐ATR and XPS analyses suggested that some reorientation had happened in synthesizing the composite latices and/or after film formation. This structure and composition endow urethane/acrylic composite films with both surface properties (such as mar‐resistance, adhesion, wettability) from pure polyurethane, and film hardness from acrylic copolymers. © 2001 Society of Chemical Industry     

Preparation and characterization of silica-supported, group IB–Pd bimetallic catalysts prepared by electroless deposition methods

Electroless deposition has been used to synthesize a series of Au–, Ag–, and Cu–Pd/SiO₂ bimetallic catalysts having incremental surface coverages and compositions of each group IB metal. Thermodynamically unstable, yet kinetically stable, electroless bath(s) were developed using metal bis-cyano salts of the group 1B metal and N₂H₄ (for Au and Ag) or DMAB (for Cu) as reducing agents. The times (1–2 h) and profiles (1st order in group 1B metal concentration) observed for complete deposition indicate good kinetic control of the electroless deposition process. The bimetallic catalysts have been characterized using selective chemisorption, atomic absorption spectroscopy (AAS), Fourier transform infrared spectroscopy (FTIR) of adsorbed CO, and X-ray photoelectron spectroscopy (XPS) techniques. Decreases in Pd surface sites with addition of IB metals confirm deposition onto the supported Pd nanoparticle surfaces. FTIR studies suggest that deposition of Cu and Ag are selective towards Pd(1 1 1) sites, while Au deposits non-discriminately on all Pd sites. Finally, XPS measurements for each family of bimetallic catalysts suggest a net electron transfer from the Pd to the deposited metal.     

Cu(II) ions removal from wastewater using starch nanoparticles (SNPs): An eco-sustainable approach

The complex structured starch particles were reduced to the nanoscale size range through hydrolysis utilizing low concentration acid assisted by ultrasound irradiation. The synthesized starch nanoparticles (SNPs) were characterized by transmission electron microscopy (TEM), Fourier-transform infrared (FTIR), and X-ray diffraction (XRD) techniques. The synthesized SNPs possessed surface activated entities, as many cationic functional groups were confirmed through the FTIR spectrum. Also, these SNPs were effectively utilized to separate heavy Cu metal ions from the synthetic ion solution. The SNPs were characterized using field emission scanning electron microscope (FESEM), X-ray photoelectron spectroscopy (XPS), and Brunauer–Emmett–Teller (BET) analysis for the surface modification after the adsorption process. The weak electrostatic interaction between the SNP surface and Cu ion was confirmed by the XPS spectrum and energy-dispersive X-ray spectroscopy. The maximum efficiency of Cu ions removal was about 93% at an optimal pH 5 and 25 mg/ml dosage. The adsorption equilibrium was obtained in 60 min. The nitrogen isotherm BET analysis of SNPs after adsorption shows a higher specific surface area of 18.552 m²/g, attributed to the interaction and presence of Cu ions on the SNP surface. The process feasibility was validated by the Langmuir isotherm model. The process exhibits pseudo-second-order adsorption kinetics and follows the Langmuir isotherm. The R_L predicted by the Langmuir isotherm mechanism is 0.017, implying favourable adsorption. The process is reproducible and allows for the separation of heavy metal ions from the wastewater through biosorption effectively.     

Surface attachment of horseradish peroxidase to nylon modified by plasma‐immersion ion implantation

The surface of polyamide (nylon 6) was modified by plasma‐immersion ion implantation (PIII) with nitrogen ions. Structural changes associated with carbonization, oxidation, and depolymerization were observed in the modified surface layer with Fourier transform infrared/attenuated total reflection (FTIR–ATR) spectroscopy, surface energy measurements, and X‐ray photoelectron spectroscopy (XPS). The enzyme activity of surface‐attached horseradish peroxidase was studied with a tetramethylbenzidine colorimetric activity assay. Compared to untreated controls, the PIII‐treated surface showed a higher level of the attached protein with increased longevity of bioactivity. Detection of the immobilized protein layer was made difficult by the presence of amide groups in nylon. Here we demonstrate the potential of combining FTIR–ATR spectroscopy with XPS measurements for this purpose. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci 120:2891–2903, 2011     

Surface modification of polyethylene by plasma pretreatment and UV‐induced graft polymerization for improvement of antithrombogenicity

The purpose of this study was to enhance blood compatibility of polyethylene (PE) films. Glycidyl methacrylate (GMA) was grafted onto the surface of PE by Ar plasma pretreatment and UV‐induced graft polymerization without photo‐initiator, then heparin was immobilized onto the poly (glycidyl methacrylate) segments. The surface compositions and microstructure of GMA graft polymerized PE films were studied by X‐ray photoelectron spectroscopy (XPS) and Attenuated Total Reflectance Fourier Transfer Infrared (ATR‐FTIR) spectroscopy. It was confirmed that heparin was successfully immobilized onto the surface of PE films by XPS analysis. The antithrombogenicity of the samples was determined by the activated partial thromboplastin time (APTT), prothrombin time (PT), thrombin time (TT), and plasma recalcification time (PRT) tests and platelet adhesion experiment. Results indicated that the antithrombogenicity of modified PE was improved remarkably. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2014–2018, 2004     

The introduction of alkyl,ester, carboxylate,amino, hydroxyl,and phosphate functional groups to the surface of polyethylene

The surface of polyethylene was derivatized with ester, carboxylate, amino, hydroxyl, and phosphate functional groups. α, ω bifunctional alkanes, containing on one end a primary amine, were coupled to oxidized polyethylene through an amide linkage. Polyethylene was first oxidized with chromic acid, the carboxylate groups were converted to the acyl chloride with phosphorus pentachloride, and then reacted with a primary amine to give the covalently bound amide. The copposing ends of the bifunctional alkanes were the methyl, tertiary amine, ester, and hydroxyl groups. The ester was converted to the carboxylate by acid cleavage and the hydroxyl group converted to the phosphate by treatment first with phosphorus oxychloride and then aqueous base. Attenuated total reflection FTIR, XPS, and pH-dependent contact angle wetting were used to characterize the surfaces. The FTIR data were used to confirm the formation of the amide and to detect an undesired carboxylate/ammonium ion complex formed in the presence of trace amounts of water. XPS data were used to confirm expected changes in elemental composition and to provide quantitative estimates of the yields. Oxidation of the polyethylene introduced 5 × 10¹⁴ carboxylate groups/cm² in the 25 Å XPS sampling depth. Of these, up to 98% could be converted to the amide. The advancing contact angle data confirmed the acid/base behavior of the functional groups.     

Surface wettability and spectroscopic studies on miscibility and ion adsorption of binary biomimetic self-assembled monolayers on gold surfaces

Binary self-assembled monolayers (SAMs) have been much studied due to their high applicable potential as a model of biomimetic surfaces. However, the research about miscibility of binary SAMs has not much been investigated yet. In this work, we focused on analyzing the binary SAMs composed of mercaptohexadecanoic acid (MHA)-hexadecanthiol (HDT) on gold surfaces with Cassie equation, Israelachvili equation, and FTIR spectroscopy to confirm that the binary SAMs are well mixed. As a result, MHA-HDT binary SAMs are considered miscible because the result obtained from FTIR spectra is in good agreement with that calculated by Israelachvili equation for the case that two different molecules are well mixed on the surface. Also, the adsorption of cadmium ions on binary SAMs was confirmed by the appearance of carboxylate stretching bands. This article is dedicated to Professor Chang Kyun Choi for celebrating his retirement from the School of Chemical and Biological Engineering, Seoul National University.     

花生壳活性炭的表征,表面改性及吸附脱除水中Pb2+离子

Metal ion contamination of drinking water and waste water, especially with heavy metal ion such as lead, is a serious and ongoing problem. In this work, activated carbon prepared from peanut shell (PAC) was used for the removal of Pb2 from aqueous solution. The impacts of the Pb2 adsorption capacities of the acid-modified carbons oxidized with HNO3 were also investigated. The surface functional groups of PAC were confirmed by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Boehm titration. The textural properties (surface area, total pore volume) were evaluated from the nitrogen adsorption isotherm at 77K. The experimental results presented indicated that the adsorption data fitted better with the Langmuir adsorption model. A comparative study with a commercial granular activated carbon (GAC) showed that PAC was 10.3 times more efficient compared to GAC based on Langmuir maximum adsorption capacity. Further analysis results by the Langmuir equation showed that HNO3 [20% (by mass)] modified PAC has larger adsorption capacity of Pb2 from aqueous solution (as much as 35.5mg.g1). The adsorption capacity enhancement ascribed to pore widening, increased cation-exchange capacity by oxygen groups, and the promoted hydrophilicity of the carbon surface.     

A comparison study of catalytic oxidation and acid oxidation to prepare carbon nanotubes for filling with Ru nanoparticles

Ru catalyst confined within the channels of multiwall carbon nanotubes (MWCNTs) is prepared by opening tube ends via mixed concentrated acid oxidation or catalytic oxidation, followed by filling via wet impregnation. The catalyst filling ratio is characterized by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The defects and functional groups are detected and quantified by Raman, fourier transformer infrared spectroscopy (FTIR) and XPS. The results show that high catalyst filling efficiency (∼80%) can be achieved with catalytic oxidation pre-treatment. The acid oxidation process can introduce more oxygen-containing functional groups such carboxyl and phenol groups. Both FTIR and XPS provide evidence for functional groups removal during thermal treatment. The effects of the nanotube length distributions, defects and functional groups on filling efficiency have been discussed intensively.     

Polymeric hydrogels obtained using a redox initiator: Application in Cu(II) ions removal from aqueous solutions

Poly(acrylic acid‐co‐acrylamide) hydrogels were prepared via free‐radical solution polymerization, crosslinked with ethylene‐glycol‐dimethacrylate, potassium persulfate/ammonium bisulfite as the initiator, and applied in the removal of Cu(II) ions from aqueous solutions. Molar ratios of acrylamide/acrylic acid moieties and the amount of crosslinking agent were varied to determine the swelling capacities of hydrogels and maximum metal uptake. Polymerization kinetics was investigated by ¹H‐NMR. Hydrogel physicochemical properties were characterized by nitrogen sorption measurements, elemental analysis, FTIR, and X‐ray photoelectron spectroscopy (XPS). Swelling results indicated that hydrogels were swollen up to 27,500%. Hydrogels showed equilibrium Cu(II) adsorption capacities of 211.7 mg g^?1 and fast kinetics (～20 min). Langmuir isotherm fitted adsorption equilibrium data. FTIR and XPS results helped in elucidating the presence of monodentate copper complex on the surface of hydrogels. A simple synthesis route of hydrogels using the redox initiator suggests the potential application in the removal of toxic metals from aqueous streams. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39933.     

Study of surface chemical changes in PVDF irradiated by 1.3 MeV electrons

Summary The chemical changes that occur on the surface of poly(vinyliden fluoride) (PVDF) irradiated with 1.3 Mev electrons at doses up to 30 MGy, were studied by X–ray photoelectron spectroscopy (XPS) and by infrared spectroscopy (FTIR) in the horizontal attenuated total reflectance mode (HATR) and in the transmission mode. The wetability of the surface before and after irradiation was measured by dynamic contact angle measurements.The C 1s structure in XPS reveals that as a result of irradiation, the –CF₂– related peak practically disappears. The remaining C 1s peak is mainly associated with C=C bonds in the heavily cross–linked carbon structure produced as a result of irradiation. FTIR spectra are consistent with the XPS observations. The irradiated films showed improvement in the oxidation and wetability of the surface.     

Poly(aspartic acid) surface modification of macroporous poly(glycidyl methacrylate) microspheres

Novel macroporous, hydrophilic microspheres with a surface layer of crosslinked poly(aspartic acid) were synthesized. In this study, macroporous poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [poly(GMA-co-EGDMA)] microspheres with pore size around 370 nm were first obtained through the surfactant reverse micelle swelling method, and the poly(GMA-co-EGDMA) was aminated by ethylene diamine to form poly(GMA-NH₂). The polysuccinimide was grafted onto the surface of poly(GMA-NH₂) microspheres and crosslinked by hexamethylendiamine and γ-aminopropyltriethoxysilane, respectively, and then hydrolyzed to obtain the poly(aspartic acid)-functionalized macroporous microspheres. The functionalized hydrophilic microspheres were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis, mercury porosimetry, and elemental analysis. The metal ion adsorption capacity was also studied. The FTIR, XPS, and elemental analysis confirmed the poly(aspartic acid) functionalization of the poly(GMA-co-EGDMA) microspheres. SEM and mercury porosimetry showed there was little effect of this surface chemical modification on microsphere porosity, and the obtained macroporous microspheres exhibited excellent thermal stability and adsorption for Ag(I), presenting great potential for applications in adsorption, fixation, and separation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47441.     

Porous silicon functionalization for possible arsenic adsorption

Thiol-functionalized porous silicon (PS) monolayer was evaluated for its possible application in As (III) adsorption. Dimercaptosuccinic acid (DMSA) attached to mesoporous silicon via amide bond linkages was used as a chelate for As (III). Two different aminosilanes namely 3-(aminopropyl) triethoxysilane (APTES) and 3-aminopropyl (diethoxy)-methylsilane (APDEMS) were tested as linkers to evaluate the relative response for DMSA attachment. The aminosilane-modified PS samples were attached to DMSA by wet impregnation followed by the adsorption of As (III). Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) have been used to identify the functional groups and to estimate the As (III) content, respectively. FTIR spectroscopy confirmed the covalent bonding of DMSA with amide and R-COOH groups on the nanostructured porous surface. XPS confirms the preferred arsenic adsorption on the surface of PS/DMSA samples as compared to the aminosilane-modified and bare PS substrates.     

Surface treatment for zinc corrosion protection by a new organic chelating reagent

The effect on the corrosion behaviour of zinc of a new organic molecule with chelating groups was investigated. Electrochemical studies of the zinc specimens were performed in aqueous sulfate–chloride solution (0.2 m Na₂SO₄ + 0.2 m NaCl, pH 5.6) using potentiostatic polarization techniques with a rotating disk electrode. Zinc samples, previously treated by immersion in the inhibiting organic solution, presented good corrosion resistance. The influence of the treatment bath pH and temperature on the protection efficiency has been emphasized. The recorded electrochemical data indicated a basic modification of the cathodic corrosion behaviour of the treated zinc resulting in a decrease of the electron transfer rate. Corrosion protection could be explained by a chelation reaction between zinc and organic molecules and the consequent growth of an organometallic layer strongly attached to the metal surface which prevented the formation of porous corrosion products in the chloride-sulfate medium. This protective film was studied using several surface analysis techniques such as X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM–EDS) and Fourier transform infrared spectroscopy (FTIR).     

Preparation and characterization of self-crosslinking fluorinated polyacrylate latexes and their pressure sensitive adhesive applications

Self-crosslinking fluorinated polyacrylate latexes based on butyl acrylate (BA), fluorine monomer octafluoropentyl methacrylate (OFPMA), self-crosslinking functional monomers acrylic acid (AA) and 2-hydroxyethyl acrylate (HEA) were synthesized by a monomer-starved seeded semi-continuous emulsion polymerization process. The latexes and their corresponding films were characterized by laser particle size analyser, Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), contact angle goniometer, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Results indicated that the particle size of the latexes and the gel content of the films were both independent of the amount of OFPMA employed. On the other hand, the particle size of the latexes decreased and the gel content of the films increased with the incorporation of AA and HEA as expected. Glass transition temperature (T_g) and the thermal stability of the copolymer were both improved gradually as OFPMA content increased. XPS, AFM and water contact angle measurement indicated that the fluoroalkyl groups had a tendency to enrich on the surface of the films. However, this enrichment of fluorine on the film surface was reduced after the introduction of self-crosslinking functional monomers into the system. Finally, the adhesive property of the latexes was evaluated for application as a pressure sensitive adhesive (PSA).     

热处理温度对对位芳纶纤维表面聚集态结构和性能影响

以不同温度(200,250,300,350℃)热处理对位芳纶纤维,用傅立叶变换红外光谱(FTIR)、拉曼光谱(Raman)、X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)分析了氧化热处理对对位芳纶纤维表面基团和聚集态结构的影响.FTIR和XRD分析结果表明,经250℃及以上热处理,纤维表层分...