Plasma-based introduction of monosort functional groups of different type and density onto polymer surfaces. Part 2: Pulsed plasma polymerization

This new functionalization method consists of the deposition of very thin plasma polymer layers (20 to 100 nm) of functional group bearing monomers in pulsed plasma. With allylalcohol, a maximum of 30 OH groups per 100 C atoms was measured with a selectivity of about 90% and a significant stability at long-time exposure to air. Allylamine was used to produce primary amino groups, with a maximum of 18 NH₂groups per 100 C atoms. Side reactions were observed during the storage in air, such as oxidation of the amino groups. Carboxylic groups could be produced using acrylic acid with a maximum concentration of 24 COOH groups per 100 C atoms. The most prominent side reaction was the decarbonylation/ decarboxylation of the acid group during plasma deposition. The variation of the density of functional groups using the pulsed-plasma polymerization of functional-group-bearing monomers was possible by the chemically-initiated radical copolymerization with either a chain-extending monomer, such as ethylene, or a cross linker, such as butadiene, in plasma. The density of functional groups could be adjusted continuously (0 to 30 OH, 0 to 18 NH₂ and 0 to 24 COOH groups per 100 C atoms). The successful application of these densely functionalized polymer surfaces for producing biocompatible surfaces and for use in metal–polymer composites is proposed.     

Study of carboxylic functionalization of polypropylene surface using the underwater plasma technique

Non-equilibrium solution plasma treatment of polymer surfaces in water offers the possibility of more dense and selective polymer surface functionalization in comparison to the well-known and frequently used low-pressure oxygen plasma. Functional groups are introduced when the polymer surface contacts the plasma moderated solution especially water solutions. The emission of ions, electrons, energy-rich neutrals and complexes, produced by the ion avalanche are limited by quenching, with the aid of the ambient water phase. The UV-radiation produced in plasma formation also helps to moderate the reaction solution further by producing additional excited, ionized/dissociated molecules. Thus, monotype functional groups equipped polymer surfaces, preferably OH groups, originating from the dissociated water molecules, could be produced more selectively. An interesting feature of the technique is its flexibility to use a wide variety of additives in the water phase. Another way to modify polymer surfaces is the deposition of plasma polymers carrying functional groups as carboxylic groups used in this work. Acetic acid, acrylic acid, maleic and itaconic acid were used as additive monomers. Acetic acid is not a chemically polymerizing monomer but it could polymerize by monomer/molecular fragmentation and recombination to a cross linked layer. The other monomers form preferably water-soluble polymers on a chemical way. Only the fragmented fraction of these monomers could form an insoluble coating by cross linking to substrate. The XPS analysis was used to track the alterations in –O-CO- bond percentage on the PP surface. To identify the -COOH groups on substrate surface unambiguously, which have survived the plasma polymerization process, the derivatization with trifluoroethanol was performed.     

Plasma polymerization investigated by the comparison of hydrocarbons and perfluorocarbons

Plasma polymerization involves to a significant extent the abstraction of atoms attached to carbons, such as hydrogen and halogen atoms, during the process of forming polymers. This abstraction reaction plays a major role in the plasma polymerization of certain groups of organic compounds. However, because of the extremely high degree of crosslinking and branching, characteristic of most plasma polymers of interest or practical value, the analysis of surfaces and/or polymers by the conventional methods is greatly hampered. Utilizing the exceptionally large chemical shifts observable in ESCA C ls spectrum of fluorcarbons, the extent of fluorine-abstraction and the rearrangement of fluorine atoms which occur during the plasma polymerization of tetrafluoroethylene were investigated using an inductive rf discharge of the monomer. The distribution of polymer deposition and the corresponding changes in properties are examined as functions of the experimental parameters. The discharge power level, which can be characterized by J/kg monomer, was found to play a predominant role in determining the physicochemical reactions which occur during the plasma polymerization. Because of the characteristic abstraction reaction which occurs in the plasma polymerization, etching by the plasma of the gas product (i.e., H₂ or F₂) plays an extremely important role in the competitive ablation and polymerization (CAP) scheme of plasma polymerization.     

Structure and photochromic properties of poly(vinylalcohol)/phosphotungstic acid nanocomposite films

Poly(vinylalcohol)/phosphotungstic acid (PVA/PWA) nanocomposite films were studied using Fourier-transform infrared and electron absorption spectroscopy. It was found that entrapping PWA into PVA leads to the formation of hydrogen bonds between OH groups of PVA and bridging oxygen atoms of PWA. Terminal oxygen atoms of PWA do not participate in hydrogen-bonding interactions with the polymer. Exposure of the nanocomposite film to UV radiation results both in the photo-induced transfer of protons from PVA to PWA with their attachment to the bridging oxygen atoms of PWA and in the formation of a PVA–PWA complex with the participation of deprotonated oxygen atoms of PVA and the terminal oxygen atoms of PWA. The UV irradiation causes the films to turn blue and a band of d–d transitions of W⁵⁺ ions (480 nm) and two bands of intervalence W⁵⁺ → W6+ charge-transfer transitions (740 and 1250 nm) to appear in their electronic spectrum.     

Fluorescence Spectroscopic Studies on Plasma-Chemically Modified Polymer Surfaces with Fluorophore-Labeled Functionalities

Molecular engineering of polymer surfaces that includes the attachment of functional molecules to existing or previously generated reactive chemical groups like e.g., − OH, − NH₂, or − CHO requires simple strategies and tools for the controlled generation of surface functionalities and their derivatization as well as for their identification and eventually quantification. Here, we systematically investigate the plasma-chemical surface modification of polypropylene films in combination with dansyl labeling chemistry and conventional, yet costly, XPS and highly sensitive fluorescence spectroscopy for the detection of surface groups. Based on these results, the potential of and requirements on the fluorometric characterization and quantification of surfaces functionalities are discussed.     

Short-time plasma surface modification of HDPE powder in a Plasma Downer Reactor - process, wettability improvement and ageing effects

The effectiveness of improving the wettability of HDPE powders within less than 0.1 s by plasma surface modification in a Plasma Downer Reactor is investigated. A correlation is revealed between the XPS results (O/C-ratio) and the wettability (contact angle, polar surface tension by capillary rise method). The O₂-content in the plasma feed gas has been adjusted for best wettability properties. XPS results indicate the formation of CO and COOH functional groups on the powder surface. The O/C-ratio increased from 0.0 (no oxygen on the non-treated powder) up to 0.15 for the plasma treated HDPE powder surface. With pure O₂-plasma treatment, a water contact angle reduction from >90° (no water penetration into the untreated PE powder) down to 65° was achieved. The total surface free energy increased from 31.2 to 45 mN/m. Ageing of treated powders occurs and proceeds mostly within the first 7 days of storage. Contact angle measurements and O1s/O2s intensity ratio data support that ageing is mainly a diffusion-controlled process. Nevertheless, XPS results show the presence of oxygen functional groups even after 40 days, which explains why the powder is still dispersible in water without any addition of surfactants.     

Investigation of the interface between polyethylene and functionalized graphene: A computer simulation study

The effect of surface chemical functionalization of a single graphene layer on its thermodynamic work of adhesion (WA) with polyethylene (PE) chains has been investigated using molecular dynamics (MD) simulation. For this purpose, amine (NH₂), carboxyl (COOH), hydroxyl (OH), and methyl (CH₃) functional groups were distributed randomly throughout the graphene surface using a Monte Carlo (MC) algorithm to achieve graphene functionalized structures with minimized potential energies. The MD simulation results showed that the thermodynamic WA between the PE and the functionalized graphene was larger than that between the PE and the pristine graphene. In fact, the electronegativity of functional groups and Van der Waals forces play influential roles in the thermodynamic WA between the PE and the functionalized graphene. In addition, the amount of thermodynamic WA was increased with increasing the functional group surface density, except for the graphene functionalized with the methyl groups. The segmental density of the PE chains near the single sheet surface was determined based on the density profile calculation. The polymer segments exhibited strong ordering and sharp density variations near the PE/graphene interface. The dynamic of chains was quantitatively characterized by calculating mean square displacement (MSD). Furthermore, the influence of functionality on the glass transition temperature (T_g) of the PE at the PE/graphene interface region was investigated. The results showed that the T_g at the PE/graphene interface was much higher than that of the bulk polymer. In fact, the functionalization of the graphene surface seems to considerably enhance the T_g of the polymer due to lowering the chains mobility.     

Grafting of polymers onto graphene oxide by cationic and anionic polymerization initiated by the surface-initiating groups

The grafting of polymers onto graphene oxide (GO) was achieved by two process: (1) cationic polymerization initiated by carboxyl (COOH) groups on GO and (2) anionic alternating copolymerization of epoxides with cyclic acid anhydrides initiated by potassium carboxylate (COOK) groups on GO. The cationic polymerizations of isobutyl vinyl ether and N-vinylcarbazole were successfully initiated by COOH groups on GO to give the corresponding polymer-grafted GO. The cationic polymerization was considered to be initiated by proton addition from COOH groups to monomer and propagation of polymer cation proceeds with carboxylate anion as a counter ion. It was found that the corresponding polymer was successfully grafted onto GO based on the termination reaction of growing polymer cation and surface counter carboxylate anion. On the other hand, the anionic ring-opening alternating copolymerization of epoxide and cyclic acid anhydrides were also initiated by COOK groups on GO, which were previously introduced onto GO by the neutralization of COOH groups with KOH. During the anionic ring-opening copolymerization of styrene oxide (SO) with phthalic anhydride (PAn) and maleic anhydride (MAn), the corresponding polyesters, poly(SO-alt-PAn) and poly(SO-alt-MAn), were successfully grafted onto GO, based on the propagation of the polyesters from COOK groups. The grafting of polymers onto GO during the above cationic and anionic polymerizations was confirmed by thermal decomposition gas chromatogram/mass spectrum. The untreated GO in THF was immediately precipitated within 15 min. On the contrary, these polymer-grafted GOs gave stable dispersions in THF and no precipitation of polymer-grafted GOs was observed even after one week.     

Applicability of chemical derivatization – X-ray photoelectron spectroscopy (CD–XPS) to the characterization of complex matrices: case of electrosynthesized polypyrroles

Problems arising in the application of XPS coupled with derivatization reactions (CD-XPS) to the characterization of complex matrices are stressed by considering the case of polypyrroles electrosynthesized from aqueous solution. In these materials oxygen– and nitrogen–carbon functionalities are contemporaneously present, as well as acidic, basic, charged and reducible groups. The derivatizing agents titanium di-isopropoxide-bis(2,4-pentanedionate) (TAA), trifluoroethanol (TFE) and pentafluorophenylhydrazine (PFPH) were used to label the C–OH, COOH and CO groups, respectively, in the pristine (PPY) and in the overoxidized (PPYox) polymer. The case shows that, when real samples are analysed, only the correlation among the information present in all the available spectra can supply the key to the interpretation of CD-XPS data, such as the actual stoichiometry and secondary effects. In particular, it is showed that PFPH cannot be used as a reliable derivatizing agent for CO groups in PPYox, due to the competition of a side reaction (already reported for hydrazines) occurring on this particular substrate. This effect may be disregarded if a thorough control of the stoichiometry is not performed.     

Investigations of Pulse‐Plasma‐Polymer Coating on TiO2 Nanoparticles and Their Dispersion

An amorphous acrylic acid (AA) polymer coating was generated on TiO₂ nanoparticles through pulse radio frequency (RF) plasma polymerization. The AA plasma synthesis mechanism was studied by its optical emission spectrum. The chemical structures of AA–plasma‐polymer were carefully investigated by Fourier transform infrared spectroscopy (FTIR). The dispersion behaviors of AA‐coated and uncoated TiO₂ nanoparticles in glycol solution were characterized by ultraviolet absorbency and particle size distribution measurements. The results showed that the aggregation of TiO₂ nanoparticles in glycol solution was effectively lowered and the dispersion was improved a lot after AA–plasma‐polymer coating. The pulse plasma coating parameters played an important role in the dispersion enhancement of TiO₂ nanoparticles. By properly regulating the pulse discharge parameters, the system could gain the highest radical–monomer reactions rate, the most compatible functional groups on the nanoparticles, and the best dispersion in the background media.     

Electronic structure of nitrogen-containing carbon nanotubes irradiated with argon ions: XPS and XANES studies

Using the methods of X-ray photoelectron (XPS) and X-ray absorption near edge structure (XANES) spectroscopies with synchrotron radiation, data on changes in the electronic structure and chemical composition of nitrogen-containing multiwalled carbon nanotubes (N-MWCNTs) upon their exposure to the radiation of argon ions with an energy of 5 keV are obtained. It is found that the exposure leads to an increase in the degree of defectiveness of the N-MWCNTs structure and to the carbon oxidation with formation of various oxygen-containing groups (C–OH, C=O/COOH, C–O–C/O–C–O, and CO₃). The presence of carbon–oxygen bonds on the surface of carbon nanotubes is associated with the formation of radiation defects. It is shown that an increase in the fraction of nitrogen atoms present in the substituting configuration in the N-MWCNTs wall structure due to the irradiation does not give rise to an increase in the density of the occupied states near the Fermi level against the background of an increase in the degree of structure defectiveness, carbon oxidation, and a decrease in the total nitrogen concentration. The obtained results show that the irradiation of N-MWCNTs with argon ions allows one to successfully functionalize their surface.

     

聚合物分子与官能化纳米管相互作用及扩散特性的分子动力学模拟

用全原子分子动力学方法研究典型聚合物分子（PE,PEO和PP）与碳纳米管（CNT）及官能化碳纳米管（FCNT）界面的相互作用及扩散特性.动力学模拟显示：—CH₃官能团具有减弱CNT与PE和PP的相互作用,但是,—CH₃官能化后的CNT与PEO之间确有增强作用.分析含氧官能团（—OH和—COOH）官能化的CNT与PE,PEO和PP的相互作用,可知含氧官能团的确具有增强表面相互作用的功能,而且含氧原子越多,相互作用就越强.此外,—CH₃,—OH,—COOH官能化后的CNT与PE,PP和PEO体系的总能量均减少,而且能量满足—COOH < —OH < —CH₃.分析非键相互作用势（库仑能和范德瓦尔斯能）,可知库伦相互作用是增强界面相互作用的主要作用能.官能化后的CNT/PE,CNT/PEO,CNT/PP体系的扩散系数都明显减小,且扩散系数大小满足—COOH < —OH < —CH₃.     

有机分子的结构与排列方式对原子电荷分布及静电作用的影响

对由两个相同的长直链分子(CH3(CH2)5—R(R=COOH,CH3,OH)、CH3(CH2)4—COOH))呈镜面对称分布组成的四种模型,及由两个CH3(CH2)5COOH分子平行分布组成的模型进行了量化计算,研究了分子间距、功能团、链长及排列方式对原子电荷分布及分子静电相互作用的影响.结果表明:1)分子中不同位置的亚甲基团(—CH2—)的C原子电荷各不相同.2)原子电荷不仅受到分子链长及功能团的影响,同时,当分子间距及排列方式发生改变时,原子电荷也发生改变;双分子模型较单分子模型的原子电荷变化较大.3)分子间静电作用由尾基功能团的极性决定,由强到弱为—COOH—OH—CH3,分子中其他原子对静电作用的贡献较小;分子链长的增加导致尾基功能团中电荷减少,从而使得分子间静电作用减弱.     

Effects of additives on palladium nanocrystals supported on multiwalled carbon nanotubes and their electrocatalytic properties toward formic acid oxidation

Carbon nanotubes are believed to be powerful materials for constructing novel hybrid composites with desirable functionalities and applications in many fields. Therefore, a better understanding of the functionalization of multiwalled carbon nanotubes (MWCNTs) holds the key to a better performance of the hybrid properties. In this paper, with a series of aromatic bifunctional molecule additives, modified MWCNTs were used as composite supports for synthesizing nanostructured palladium catalysts for formic acid oxidation. The additives contain anthranilic acid, o-phenylenediamine, salicylic acid, catechol, and phthalic acid. The influence of the different bifunctional groups (such as –NH₂, –OH, –COOH, and their mixed groups) on the morphologies, particle sizes, and electrical properties of Pd nanocrystals was intensively studied. Transmission electron microscopy measurement demonstrates that the palladium nanoparticles were well dispersed on the surface of MWCNTs with a relatively narrow particle size distribution in the presence of the additives. Cyclic voltammetry and chronoamperometry tests demonstrate that the functional groups of the additives play an important role in electrocatalytic activity and stability for formic acid oxidation, and the influence law of various functional groups on electrocatalytic activity and stability is also investigated in this paper. We hope it can provide certain theoretical guidance meaning and practical reference value in future studies.     

COOH-functionalisation of silica particles

In this study COOH-functionalised silica is synthesised using phosphonateN-(phosphonomethyl)iminodiacetic acid (PMIDA) in an aqueous solution. The presence of PMIDA on the silica particles was verified using Fourier Transform Infrared Spectroscopy, X-ray Photoelectron Spectroscopy and titration. Experimentally, surface concentrations of COOH functional groups of up to about 3 mmol/g_silica were achieved, whereas theoretical calculation of the maximum COOH functional group concentration gave about 1 mmol/g_silica. The discrepancy may be caused by PMIDA multilayer formation on the particle.     

The aging of atmospheric plasma-treated ultrahigh-modulus polyethylene fibers

The aging effects of atmospheric plasma treatments on UHMPE fibers are studied. UHMPE fibers are treated for 0.5 and 1 min with He/O₂/air gas and for 2 and 4 min with He/air gas by atmospheric pressure plasma on a capacitively coupled device at a frequency of 5 kHz. The samples are tested for fiber/epoxy interfacial shear strength at time intervals of 0, 3, 15 and 30 days after initial plasma treatment. Scanning electron microscopy shows micro-cracks on each set of treated fibers, which is not affected by aging over the 30 day study. Interfacial shear strengths (IFSS) for plasma-treated fibers are 2–3 times as high as that of the control. The IFSS for the plasma treated fibers remains constant up to 15 days and then decreases afterwards. XPS Analysis shows a slight increase in atomic concentration of oxygen and nitrogen for each plasma-treated sample. For the He/O₂/air plasma-treated samples, XPS analysis shows an observable increase in C–OH bonds, C=O bonds and COOH bonds, while for the He/air plasma-treated samples, there is a slight increase in C–OH and O=C–O bonds. After 30 days, a decrease in oxygen content for all plasma-treated samples is manifested.     

Functional groups grafted nonwoven fabrics for blood filtration—The effects of functional groups and wettability on the adhesion of leukocyte and platelet

In this work, the effects of grafted functional groups and surface wettability on the adhesion of leukocyte and platelet were investigated by the method of blood filtration. The filter materials, poly(butylene terephthalate) nonwoven fabrics bearing different functional groups including hydroxyl (OH), carboxyl (COOH), sulfonic acid group (SO₃H) and zwitterionic sulfobetaine group (^⊕N((CH₃)₂)(CH₂)₃SO₃^?) with controllable wettability were prepared by UV radiation grafting vinyl monomers with these functional groups. Our results emphasized that both surface functional groups and surface wettability had significant effects on the adhesion of leukocyte and platelet. In the case of filter materials with the same wettability, leukocytes adhering to filter materials decreased in the order: the surface bearing OH only > the surface bearing both OH and COOH > the surface bearing sulfobetaine group > the surface bearing SO₃H, while platelets adhering to filter materials decreased as the following order: the surface bearing SO₃H > the surface bearing both OH and COOH > the surface bearing OH only > the surface bearing sulfobetaine group. As the wettability of filter materials increased, both leukocyte and platelet adhesion to filter materials declined, except that leukocyte adhesion to the surface bearing OH only remained unchanged.     

Optical study of radicals (OH,O, H,N) in a needle-plate bi-directional pulsed corona discharge

In this study, analysis of optical emission spectra are used for the detection of OH (A²Σ) radicals and O (3p⁵P), H_α (3P) and N (3p⁴P) active atoms produced by the high-voltage bi-directional pulsed corona discharge of N₂ and H₂O mixture gas in a needle-plate reactor at one atmosphere. The relative vibrational populations and the vibrational temperature of N₂ (C, v') are determined. The effects of pulse peak voltage, pulse repetition rate and the added O₂ flow rate on the relative populations of OH (A²Σ) radicals and O (3p⁵P), H_α (3P) and N (3p⁴P) active atoms are investigated. It is found that when pulse peak voltage and pulse repetition rate are increased, the relative populations of those excited states radicals rise correspondingly. The relative population of OH (A²Σ) radicals decreases with increasing the flow rate of oxygen. The relative populations of O (3p⁵P), H_α (3P) and N (3p⁴P) active atoms increase with the flow rate of oxygen at first and exhibit a maximum value at about 30 ml/min. When the flow rate of oxygen is increased further, the relative populations of those excited states active atoms decrease correspondingly. The main involved physicochemical processes also have been discussed.     

胶体金核壳型沙丁胺醇分子印迹聚合物的光谱特征分析

为了解决饲料和动物产品中沙丁胺醇残留现场快速检测的难题,开发以分子印迹技术为基础的快速检测沙丁胺醇的新方法,使用沙丁胺醇做为模板分子,甲基丙烯酸(methacrylic acid, MA)作为功能单体,以本体聚合法为基础合成常规SAL分子印迹聚合物（molecularly imprinted polymer,MIPs）和非分子印迹聚合物（non imprinted polymer NIPs）。在此基础上,以胶体金粒子为引发核,制备出新型的核壳型沙丁胺醇MIPs。应用紫外吸收光谱(UV spectra)、傅里叶红外光谱(IR spectra)和拉曼光谱（Raman spectru）、扫描电镜（scanning electron microscopy,SEM）等技术手段获得两种印迹物及各种相关化合物的光谱图、电镜图等表征图像。由实验结果可知,SAL和MA上的羧基形成稳定又容易洗脱的1∶1型氢键配合物,化学结合常数K=-0.245×106 L2·mol-2。与MA的—COOH中氢原子形成氢键的可能结合位点是SALCO中的氧原子。MIPs与MA中—OH的吸收峰比较可知,前者明显红移; 证明SAL作为模板分子与MA之间发生特定结合。未洗脱MIPs的CO的伸缩振动产生的吸收峰红移; 即能量损失明显,可知MA中—COOH的氢原子如果要生成氢键,可能的结合位点就是SAL分子内CO中的氧原子。MIPs和NIPs中CC, CO, —OH等吸收明显的官能团峰型大致相同。将MIPs洗脱掉作为模板分子的SAL后,留下了含有特殊且确定结构官能团化学及空间构成均与SAL高度匹配的空穴, 可与待测液中的目标检测分子SAL发生特异性识别和专一结合作用。而胶体金核壳型MIPs与常规MIPs相比,除具有以上相同特点外,其表面更加松散,表面孔穴明显增多。由此增加了吸附目标分子的有效面积,具有更优良的吸附性能。这两种印迹物的合成及光谱特征分析为建立基于分子印迹技术的快速检测SAL新方法奠定了理论和实践基础。     

An XPS study of the water adsorption on Cu(110)

The adsorption of H₂O on clean and oxygen precovered Cu(110) is studied at temperatures between 90 and 300 K by XPS. On the oxygen precovered surface three O(1s) emission lines are detected at lower temperature. They originate from adsorbed atomic oxygen, from OH groups, and from H₂O molecules. For an oxygen coverage of half a monolayer, XPS indicates that during H₂O decomposition the preadsorbed oxygen does not directly participate in the OH formation. After water adsorption on the clean surface three O(1s) emission lines are found, which are due to H₂O molecules, “disturbed” H₂O molecules, and OH groups. The XPS results are directly correlated with information about the adsorbates obtained by UPS. Coverages are determined from the XPS spectra for the detected species.