Properties and characterization of hydrophobized microfibrillated cellulose

Microfibrillated cellulose (MFC) obtained by disintegration of bleached softwood sulphite pulp in a homogenizer, was hydrophobically modified by surface silylation with chlorodimethyl isopropylsilane (CDMIPS). The silylated MFC was characterized by Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM), transmission electron spectroscopy (TEM), X-ray photoelectron spectroscopy (XPS) and white light interferometry (WLI). The degree of surface substitution (DSS) was determined using Si concentrations from XPS survey scans, as well as deconvoluted peaks in high-resolution C1s XPS spectra. The DSS values obtained by the two methods were found to be in good agreement. MFC with DSS between 0.6 and 1 could be dispersed in a non-flocculating manner into non-polar solvents, TEM observations showing that the material had kept its initial morphological integrity. However, when CDMIPS in excess of 5 mol CDMIPS/glucose unit in the MFC was used, partial solubilization of the MFC occurred, resulting in a drop in the observed DSS and a loss of the microfibrillar character of the material. The wetting properties of films cast from suspension of the silylated MFC were also investigated. The contact angles of water on the films increased with increasing DSS of the MFC, approaching the contact angles observed on super hydrophobic surfaces for the MFC with the highest degree of substitution. This is believed to originate from a combination of low surface energy and surface microstructure in the films.     

Hydrophobic modification of cellulose nanocrystal via covalently grafting of castor oil

Hydrophobic cellulose nanocrystals (CNs) have been prepared by grafting isocyanate-terminated castor oil, a kind of natural vegetable oil, onto their surface. The existence of castor oil component in the modified cellulose nanocrystals was verified by Fourier transform infrared spectroscopy, solid-state ¹³C NMR spectra and X-ray photoelectron spectroscopy. At the same time, X-ray diffraction and transmission electron micrographs further proved that the crystalline structure and large aspect ratio of cellulose nanocrystals were essentially preserved after chemical grafting. Furthermore, the surface of modified cellulose nanocrystals appeared to be hydrophobic as indicated by contact angle measurements. The value of the polar component of surface energy decreased from 21.5 mJ/m² to almost zero via grafting castor oil. These novel hydrophobic castor oil-grafted cellulose nanocrystals appear as valuable alternatives to formulate bionanocomposites with non-polar polymers for optimized performances.     

Elemental composition analysis of silicon carbonitride thin films by energy dispersive spectroscopy

Specific features of elemental composition analysis of silicon carbonitride thin films by energy dispersive spectroscopy (EDS) are considered. The films were preliminarily examined by IR spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron (SEM) and atomic force microscopy (AFM), and X-ray diffraction analysis using synchrotron radiation (SR-XRD) to acquire data on their chemical and phase composition, crystalline structure and surface morphology. The effect of film thickness, substrate material and electron beam energy on the results of energy dispersive analysis was investigated.     

A study of atmospheric-pressure CHF3/Ar plasma treatment on dielectric characteristics of polyimide films

In this work, the influence of atmospheric-pressure CHF(3)/Ar plasma treatment on surface dielectric properties of polyimide films was investigated using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and contact angle measurements. The dielectric characteristics of the films were studied using a dielectric spectrometer. From the results, it was found that the plasma treatment introduced fluorine functional groups onto the polyimide surfaces. F 1s/C 1s ratios of the polyimides were enhanced with the increase of plasma treatment time. Consequently, the fluorine groups led to a decrease of the surface free energy and dielectric constant of the polyimide films, which can largely be attributed to the decrease of the deformation polarizability or London dispersive component of surface free energy of the solid surface studied.     

Wettability and surface composition of partly and fully regenerated cellulose thin films from trimethylsilyl cellulose

The wettability and surface free energy (SFE) of partly and fully regenerated cellulose model surfaces from spin coated trimethylsilyl cellulose were determined by static contact angle (SCA) measurements. In order to gain detailed insight into the desilylation reaction of the surfaces the results from SCA measurements were compared with data from other surface analytical methods, namely thickness measurements, X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance infrared spectroscopy (ATR-IR). Additionally, the influence of ultra high vacuum treatment (UHV) during XPS measurements on the water wettability and surface morphology of regenerated cellulose thin films was investigated. The wetting of polar and non-polar liquids increased with prolonged regeneration time, which is reflected in the higher SFE values and polarities of the films. After UHV treatment the water SCA of partly regenerated films decreases, whereas fully regenerated cellulose shows a higher water SCA. Therefore it is assumed that volatile desilylation products tend to adsorb on partly regenerated films, which strongly influences their wettability.     

Surface chemical modification of microfibrillated cellulose: improvement of barrier properties for packaging applications

Heterogeneous acetylation of microfibrillated cellulose (MFC) was carried out to modify its physical properties and at the same time to preserve the morphology of cellulose fibrils. The overall reaction success was assessed by FTIR together with the degree of substitution (DS) defined by titration and the degree of surface substitution (DSS) evaluated by means of XPS. Dynamic contact angle measurements confirmed the hydrophobicity improvement relative to non-modified samples. The increase of contact angle upon reaching a certain reaction time and some decrease following the further acetylation was confirmed. Mechanical properties of MFC films made from chemically modified material were evaluated using tensile strength tests which showed no significant reduction of tensile strength. According to SEM images, dimension analysis and tensile strength data, the acetylation seemed not to affect the morphology of cellulose fibrils.     

Cationic wood cellulose films with high strength and bacterial anti-adhesive properties

In this work, periodate oxidized birch wood pulp and microfibrillated cellulose (MFC) were cationized using Girard’s reagent T or aminoguanidine. Cationic celluloses were used to obtain films via solvent-casting method, and the effects of the cationization route and the cellulose fiber source on the properties of the films were studied. Thermal and optical properties of the films were measured using differential scanning calorimetry and UV–Vis spectrometry, and the morphology of the films was examined using an optical microscope and a field emission scanning electron microscope. Bacterial anti-adhesive properties of the films were also studied using a modified leaf print method and against Staphylococcus aureus and Escherichia coli. Both cationizing agents exhibited similar reactivity with periodate oxidized celluloses, however, MFC had significantly higher reactivity compared to birch pulp. The films with high tensile strength (39.1–45.3 MPa) and modulus (3.5–7.3 GPa) were obtained from cationized birch pulp, aminoguanidine modification producing a film with slightly better mechanical properties. Modulus of the films was significantly increased (up to 14.0 GPa) when MFC was used as a cellulose fiber source. Compared to the unmodified MFC films, the cationic MFC films were less porous and significantly more transparent; however, they had slightly lower tensile strength values. It was found that aminoguanidine modified celluloses had no culturable bacteria on its surface and also exhibited resistance to microbial degradation, whereas there were culturable bacteria on the surface of Girard’s reagent modified films and they were partially degraded by the bacteria.     

Reduction of water wettability of nanofibrillated cellulose by adsorption of cationic surfactants

Adsorption isotherms of single and double chain cationic surfactants with different chain length (cetyltrimethyl-, didodecyl- and dihexadecyl ammonium bromide) onto cellulose nanofibrils were determined. Nanofibrillated cellulose, also known as microfibrillated cellulose (MFC), with varying contents of carboxyl groups (different surface charge) was prepared by TEMPO-mediated oxidation followed by mechanical fibrillation. The fibril charge was characterized by potentiometric and conductometric titration. Surfactant adsorption was verified by Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS). Wetting and adhesion of water onto fibril films was determined by contact angle measurements. Small aggregates (admicelles) of surfactant were shown to form on the nanofibril surfaces, well below critical micelle concentrations. The results demonstrate the possibility of using cationic surfactants to systematically control the degree of water wettability of cellulose nanofibrils.     

Multi-instrument characterization of HiPIMS and DC magnetron sputtered tungsten and copper films

In this work, copper and tungsten were sputtered onto silicon wafers by direct current magnetron sputtering (DCMS) and high-power impulse magnetron sputtering (HiPIMS). The resulting films were characterized by energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and X-ray diffraction (XRD). By EDX and XPS, all the sputtered films showed only the expected metal peaks. By XPS, the surfaces sputtered by DCMS were richer in oxygen than those produced by HiPIMS. By AFM, the surfaces were quite smooth. The root mean square (RMS) roughness values are as follows: 0.83 nm (W, HiPIMS), 1.10 nm (W, DCMS), 0.85 nm (Cu, HiPIMS), and 1.78 nm (Cu, DCMS). By SEM, the HiPIMS films exhibited smaller grain sizes, which was confirmed by XRD. The crystallite sizes estimated by XRD are as follows: 4 nm (W, body-centered cubic, HiPIMS), 13 nm (W, body-centered cubic, DCMS), 7 nm (W, cubic, HiPIMS), 14 nm (W, cubic, DCMS), 25 nm (Cu, HiPIMS), and 35 nm (Cu, DCMS). By SE, the HiPIMS surfaces showed higher refractive indices, which suggested that they were denser and less oxidized than the DCMS surfaces.     

Comparison of nano- and microfibrillated cellulose films

Nanocellulose is an interesting building block for functional materials and has gained considerable interest due to its mechanical robustness, large surface area and biodegradability. It can be formed into various structures such as solids, films and gels such as hydrogels and aerogels and combined with polymers or other materials to form composites. Mechanical, optical and barrier properties of nanofibrillated cellulose (NFC) and microfibrillated cellulose (MFC) films were studied in order to understand their potential for packaging and functional printing applications. Impact of raw material choice and nanocellulose production process on these properties was evaluated. MFC and NFC were produced following two different routes. NFC was produced using a chemical pretreatment followed by a high pressure homogenization, whereas MFC was produced using a mechanical treatment only. TEMPO-mediated oxidation followed by one step of high pressure (2,000 bar) homogenization seems to produce a similar type of NFC from both hardwood and softwood. NFC films showed superior mechanical and optical properties compared with MFC films; however, MFC films demonstrated better barrier properties against oxygen and water vapor. Both the MFC and NFC films were excellent barriers against mineral oil used in ordinary printing inks and dichlorobenzene, a common solvent used in functional printing inks. Barrier properties against vegetable oil were also found to be exceptionally good for both the NFC and MFC films.     

Surface characterization of cellulose fibres by XPS and inverse gas chromatography

Inverse gas chromatography (IGC) was used to determine the dispersive component of the free energy as well as the acid-base properties of cellulose fibre surfaces, before and after modification by corona treatment. It was found that the corona treatment increases both the dispersive contribution to surface energy and its acidic character, whereas only a slight increase in its basicity was observed. It was also found that some chemical degradation of the surface occurs at high corona currents. The extent of modification of the surface properties, as revealed by IGC, was correlated to the surface chemical composition deduced from XPS analysis as well as with the electrical conductance and the pH of the water suspensions of the cellulose fibres.     

Chemical surface modifications of microfibrillated cellulose

Microfibrillated cellulose (MFC) was prepared by disintegration of bleached softwood sulphite pulp through mechanical homogenization. The surface of the MFC was modified using different chemical treatments, using reactions both in aqueous- and organic solvents. The modified MFC was characterized with fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Epoxy functionality was introduced onto the MFC surface by oxidation with cerium (IV) followed by grafting of glycidyl methacrylate. The length of the polymer chains could be varied by regulating the amount of glycidyl methacrylate added. Positive charge was introduced to the MFC surface through grafting of hexamethylene diisocyanate, followed by reaction with the amines. Succinic and maleic acid groups could be introduced directly onto the MFC surface as a monolayer by a reaction between the corresponding anhydrides and the surface hydroxyl groups of the MFC.     

Interfacial properties of cellulose nanoparticles obtained from acid and enzymatic hydrolysis of cellulose

Rod-shaped cellulose nanocrystals obtained by acid hydrolysis of eucalyptus fibers (CNCa) presented high aspect ratio (estimated length and width of 180 and 5 nm, respectively) and zeta potential of ?(17 ± 1) mV at pH 6. This typical morphology of cellulose nanocrystals was in contrast to nanoparticles obtained upon enzymatic hydrolysis of bacterial cellulose (CNCe), which were asymmetric and irregular due to surface-bound cellulases and presented a distinctive surface roughness. Interestingly, CNCe also displayed axial grooves, to yield a C-shape cross section that has not been reported before. The effect of the characteristic shape and surface chemistry of CNCa and of grooved CNCe was studied at oil/water interfaces and solid surfaces. Emulsions (20 % v/v oil) prepared with the CNCa were more stable than those prepared with CNCe, owing to their characteristic shape and surface chemistry. Hydrophilic (silica surfaces cationized by pre-adsorbed polycation) and hydrophobic (polystyrene films) solid surfaces were used as substrates for the adsorption of CNCe and CNCa for each type of surface. The ellipsometric data and AFM images indicated larger affinity of CNCe than CNCa for the hydrophobic surface. On the other hand, CNCa formed homogeneous monolayer on hydrophilic surfaces, whereas CNCe formed discontinuous films. Sequential adsorption behavior of CNCa on CNCe layers (or vice versa) suggested that the interaction between them is controlled by the orientation of enzymes bound to CNCe.     

聚(二甲基硅氧烷-co-甲氧基十二烷基硅氧烷)在棉纤维及其模型表面的膜形貌及定向排列方式

用场发射扫描电镜(FESEM)、原子力显微镜(AFM)、光电子能谱(XPS)等仪器研究了棉纤维以及再生纤维素表面聚(二甲基硅氧烷-co-甲氧基十二烷基硅氧烷)(DDPS)的膜形貌及其定向排列方式.结果发现,在天然棉纤维以及再生纤维素模型表面,DDPS均能形成宏观上平滑、而微观形态学实则非均一的疏水性硅膜,表明DDPS的定向排列成膜方式为疏水性硅甲基、硅十二烷基朝外伸向空气,硅氧偶极键指向基质界面.     

Enhanced TiO2 surface electrochemistry with carbonised layer-by-layer cellulose-PDDA composite films

In this report we demonstrate a versatile (and potentially low-cost) cellulose nano-whisker-based surface carbonisation method that allows well-defined films of TiO(2) nanoparticles surface-modified with carbon to be obtained. In a layer-by-layer electrostatic deposition process based on TiO(2) nanoparticles, cellulose nano-whiskers, and poly(diallyl-dimethylammonium) or PDDA are employed to control the ratio of surface carbon to TiO(2). Characterisation based on optical, AFM, XRD, and XPS methods is reported. Electrochemical measurements suggest improved access to surface states, dopamine binding at the anatase surface, and surface redox cycling aided by the thin amorphous carbon film in mesoporous TiO(2). In future, the amorphous carbon layer method could be applied for surface processes for a wider range of semiconductor or insulator surfaces.     

Roughness effects of cellulose and paper substrates on water drop impact and recoil

The impact dynamics of water drops on sized and unsized smooth cellulose films and paper surfaces with controlled roughness levels were studied. The objective was to better understand the effect of roughness on the liquid drop impact dynamics on paper surfaces, isolating from the effect chemical heterogeneity. Drop impact in the first few milliseconds were recorded using high-speed CCD camera and the three-phase contact line movement of the water drop was analyzed. Smooth cellulose film surface and rough paper surface showed similar impact dynamics, suggesting that the surface energy plays a more dominant role than surface roughness. Significantly different dynamic contact angles of water drop on the sized and unsized surfaces were observed during drop impact. The Laplace pressure of the curved spreading front pointing to the centre of a spreading drop on these sized cellulose and paper surfaces reduces the three-phase contact line movement, and leads to smaller maximum spreading diameter. Our results suggest that the water drop spreads on the rough surface is most likely via a “roll-over” action rather than “stick and jump” movements.     

Surface characterization of 3-glycidoxypropyltrimethoxysilane films on silicon-based substrates

Silane coupling agents are commonly used to activate surfaces for subsequent immobilization of biomolecules. The homogeneity and surface morphology of silane films is important for controlling the structural order of immobilized single-stranded DNA probes based on oligonucleotides. The surfaces of silicon wafers and glass slides with covalently attached 3-glycidoxypropyltrimethoxysilane (GOPS) have been characterized by using angularly dependent X-ray photoelectron spectroscopy (XPS), time-of-flight secondary-ion mass spectrometry (ToF–SIMS), atomic force microscopy (AFM), scanning electron microscopy (SEM), and monochromatic and spectroscopic ellipsometry. XPS and ToF–SIMS data provided evidence of complete surface coverage by GOPS. Data from angularly resolved XPS and ellipsometry methods suggested that the GOPS films were of monolayer thickness. AFM and SEM data indicated the presence of films that consisted of nodules approximately 50–100 nm in diameter. Modeling suggested that the nodules may lead to a nanoscale structural morphology that might influence the hybridization kinetics and thermodynamics of immobilized oligonucleotides.     

Dendrimer-functionalized self-assembled monolayers as a surface plasmon resonance sensor surface

We report here a multistep route for the immobilization of DNA and proteins on chemically modified gold substrates using fourth-generation NH(2)-terminated poly(amidoamine) dendrimers supported by an underlying amino undecanethiol (AUT) self-assembled monolayer (SAM). Bioactive ultrathin organic films were prepared via layer-by-layer self-assembly methods and characterized by fluorescence microscopy, variable angle spectroscopic ellipsometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and attenuated total internal reflection Fourier transform infrared spectroscopy (ATR-FTIR). The thickness of the AUT SAM base layer on the gold substrates was determined to be 1.3 nm from ellipsometry. Fluorescence microscopy and AFM measurements, in combination with analyses of the XPS/ATR-FTIR spectra, confirmed the presence of the dendrimer/biopolymer molecules on the multilayer sensor surfaces. Model proteins, including streptavidin and rabbit immunoglobulin proteins, were covalently attached to the dendrimer layer using linear cross-linking reagents. Through surface plasmon resonance measurements, we found that sensor surfaces containing a dendrimer layer displayed an increased protein immobilization capacity, compared to AUT SAM sensor surfaces without dendrimer molecules. Other SPR studies also revealed that the dendrimer-based surfaces are useful for the sensitive and specific detection of DNA-DNA interactions. Significantly, the multicomponent films displayed a high level of stability during repeated regeneration and hybridization cycles, and the kinetics of the DNA-DNA hybridization process did not appear to be influenced by surface mass transport limiting effects.     

Surface modification of EPDM rubber by plasma treatment

The effect of argon, oxygen, and nitrogen plasma treatment of solvent cast EPDM rubber films has been investigated by means of atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and surface energy measurements. Plasma treatment leads to changes in the surface energy from 25 to 70 mN/m. Treatment conditions influenced both the changes in surface energy and the stability, and it became more difficult to obtain good contact angle measurements after longer (> ca. 4 min) treatment times, probably because of an increasingly uneven surface structure. XPS analyses revealed that up to 20 at. % oxygen can be easily incorporated and that variations of approximately 5% can be controlled by the plasma conditions. Oxygen was mainly found in hydroxyl groups, but also as carbonyl and carboxyl. XPS analyses showed more stable surfaces than expected from contact angles, probably because XPS analysis is less surface sensitive than contact angle measurements. AFM measurements revealed different surface structures with the three gases. The surface roughness increased generally with treatment time, and dramatic changes could be observed at longer times. At short times, surface energy changes were much faster than the changes in surface structure, showing that plasma treatment conditions can be utilized to tailor both surface energies and surface structure of EPDM rubber.     

Surface modification of low-density polyethylene by inductively coupled argon plasma

The surface chemistry and nanotopography of low-density polyethylene (LDPE) were modified by downstream, inductively coupled, radio frequency (rf) Ar plasma without inducing surface damage. The extent of surface modification was controlled by the applied ion energy fluence, determined from the plasma ion density measured with a Langmuir probe. The treated LDPE surfaces were characterized by atomic force microscope (AFM) imaging, contact angle measurements, and X-ray photoelectron spectroscopy (XPS). Analysis of AFM surface images confirmed that topography changes occurred at the nanoscale and that surface damage was insignificant. Contact angle measurements demonstrated an enhancement of the surface hydrophilicity with the increase of the plasma power. XPS results showed surface chemistry changes involving the development of different carbon-oxygen functionalities that increased the surface hydrophilicity. Physical and chemical surface modification was achieved under conditions conducive to high-density inductively coupled rf plasma.