Electrospinning of ultrafine cellulose acetate fibers: Studies of a new solvent system and deacetylation of ultrafine cellulose acetate fibers

Electrospinning of cellulose acetate (CA) in a new solvent system and the deacetylation of the resulting ultrafine CA fibers were investigated. Ultrafine CA fibers (∼2.3 μm) were successfully prepared via electrospinning of CA in a mixed solvent of acetone/water at water contents of 10–15 wt %, and more ultrafine CA fibers (0.46 μm) were produced under basic pH conditions. Ultrafine cellulose fibers were regenerated from the homogeneous deacetylation of ultrafine CA fibers in KOH/ethanol. It was very rapid and completed within 20 min. The crystal structure, thermal properties, and morphology of ultrafine CA fibers were changed according to the degree of deacetylation, finally to those of pure cellulose, but the nonwoven fibrous mat structure was maintained. The activation energy for the deacetylation of ultrafine CA fibers was 10.3 kcal/mol. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 5–11, 2004     

All-cellulose nanocomposite fibers produced by melt spinning cellulose acetate butyrate and cellulose nanocrystals

Bio-based continuous fibers were prepared by melt spinning cellulose acetate butyrate (CAB), cellulose nanocrystals (CNC) and triethyl citrate. A CNC organo-gel dispersion technique was used and the prepared materials (2 and 10 wt% CNC) were melt spun using a twin-screw micro-compounder and drawn to a ratio of 1.5. The microscopy studies showed that the addition of CNC in CAB resulted in defect-free and smooth fiber surfaces. An addition of 10 wt% CNC enhanced the storage modulus and increased the tensile strength and Young’s modulus. Fiber drawing improved the mechanical properties further. In addition, a micromechanical model of the composite material was used to estimate the stiffness and showed that theoretical values were exceeded for the lower concentration of CNC but not reached for the higher concentration. In conclusion, this dispersion technique combined with melt spinning can be used to produce all-cellulose nanocomposites fibers and that both the increase in CNC volume fraction and the fiber drawing increased the mechanical performance.     

Photodegradation of poly(vinyl acetate)

Poly(vinyl acetate) (PVAc) films with different molecular masses were exposed to ultraviolet radiation. The infra-red spectra of all the samples showed a continuous attenuation of the intensity of the carbonyl stretching bands (1740 cm⁻¹) and of the symmetrical methyl bending vibration bands (1375 cm⁻¹), which suggests a steady loss of acetate side groups during irradiation.The electronic spectra showed an increase in the uv absorption at about 272 nm, suggesting the occurrence of polyene sequences in the polymer chains.In the low molecular mass sample there was almost no insoluble gel fraction formed, even after 20 h irradiation; in the high molecular mass polymer there was already a 50% insoluble fraction after 5 h irradiation, indicating a high degree of crosslinking, although the average viscometric molecular mass of the soluble fraction was only about one sixth of the initial value.     

Electrospun cellulose acetate fibers: effect of solvent system on morphology and fiber diameter

This paper reports an investigation of the effects of solvent system, solution concentration, and applied electrostatic field strength (EFS) on the morphological appearance and/or size of as-spun cellulose acetate (CA) products. The single-solvent systems were acetone, chloroform, N,N -dimethylformamide (DMF), dichloromethane (DCM), methanol (MeOH), formic acid, and pyridine. The mixed-solvent systems were acetone–DMAc, chloroform–MeOH, and DCM–MeOH. Chloroform, DMF, DCM, MeOH, formic acid, and pyridine were able to dissolve CA, forming clear solutions (at 5% w/v), but electrospinning of these solutions produced mainly discrete beads. In contrast, electrospinning of the solution of CA in acetone produced short and beaded fibers. At the same solution concentration of 5% (w/v) electrospinning of the CA solutions was improved by addition of MeOH to either chloroform or DCM. For all the solvent systems investigated smooth fibers were obtained from 16% (w/v) CA solutions in 1:1, 2:1, and 3:1 (v/v) acetone–DMAc, 14–20% (w/v) CA solutions in 2:1 (v/v) acetone–DMAc, and 8–12% (w/v) CA solutions in 4:1 (v/v) DCM–MeOH. For the as-spun fibers from CA solutions in acetone–DMAc the average diameter ranged between 0.14 and 0.37 μm whereas for the fibers from solutions in DCM–MeOH it ranged between 0.48 and 1.58 μm. After submersion in distilled water for 24 h the as-spun CA fibers swelled appreciably (i.e. from 620 to 1110%) but the physical integrity of the fibrous structure remained intact.     

Thermochromic cellulose fibers

A method of obtaining thermochrome cellulose fibers has been developed. The basis technology used to form fibers was the Lyocell process. This method is based on spinning fibers from concentrated solvents of cellulose, using dry‐wet method in aqueous solidification bath. The cellulose solvent used in this process was N‐oxide‐N‐methylomorpholine (NMMO). The studies were to check on the features of the fibers obtained from solvents with thermochrome pigmentation, in order to evaluate their practical use. Thermochrome modifier used in the experiment was Chromicolor®AQ‐INK, Magenta type#27 pigmentation. This modifier was introduced into the spinning solutions in such amounts that fibers obtained from them would contain 1–10 wt% of pigmentation. Fibers formed out of modified solvents underwent spectral values, thermal, physicomechanical analyses, also their sorption features were evaluated. Copyright © 2007 John Wiley & Sons, Ltd.     

Effect of take-up speed on physical properties and permeation performance of cellulose acetate hollow fibers

Cellulose acetate (CA) ultrafiltration hollow fibers were spun via the dry-jet wet spinning technique. The effect of the take-up speed on the mechanical properties, morphology, thermal properties, pure water permeation, retention, and surface characterization of hollow fiber membranes were investigated. Both the inner and outer diameters of the hollow fiber decreased with the increase of take-up speed. Macrovoids were observed on the inner surface of the drawn hollow fibers. The d-space decreased with the increase of the take-up speed. The ultimate tensile stress (UTS) increased and the breaking elongation decreased with the increase of take-up speed. The permeation performance was measured. The hydraulic permeability increased and the retention decreased slightly with the increase of the take-up speed. The surface roughness increased with the increase of the take-up speed. The thermal analysis results showed that the endothermic peak shifts to the higher temperature region and coefficient of thermal expansion (CTE) decrease for a higher take-up speed.     

Preparation and characterization of electrospun fibers based on poly(L-lactic acid)/cellulose acetate

PLLA/CA mixtures of different compositions were successfully electrospun to obtain composite nanofibrous membranes.The microstructures of the membrances changed from homogeneous to heterogeneous with the addition of CA, which was observed by FE-ESEM.The PLLA/CA fabric membranes were characterized by mechanical testing,DSC and contact angle measurements.The tensile stress of the composite fibrous membranes increased obviously with the increase of CA content.DSC results indicated that the CA component was the main factor for the changes of enthalpies in the composite fibers.Contact angle measurements showed the hydrophilicity of the electrospun nanofiber membranes was improved with the addition of CA.     

纤维素醋酸酯的均相合成

纤维素的非均相反应取代不均匀、产率低。本文用纤维素在LiCl／DMAc溶液中的均相反应。制得了纤维素三醋酸酯(CTA)、纤维素二醋酸酯(CDA)、纤维素—醋酸酯(CMA),并对产品结构性能进行了表征。     

Ultrafine fibrous cellulose membranes from electrospinning of cellulose acetate

Three solvents, that is, acetone, acetic acid, and dimethylacetamide (DMAc), with a range of solubility parameter δ, surface tension γ, viscosity η and boiling temperature were used to generate mixtures for electrospinning cellulose acetate (CA) (degree of substitution, DS = 2.45). Although none of these solvents alone enables continuous formation of fibers, mixing DMAc with either acetone or acetic acid produced suitable solvent systems. The 2:1 acetone:DMAc mixture is the most versatile mixture because it allows CA in the 12.5–20% concentration range to be continuously electrospun into fibrous membranes. These CA solutions have η between 1.2 and 10.2 poise and γ around 26 dyne/cm and produce smooth fibers with diameters from 100 nm to ～1 μm. Fiber sizes generally decrease with decreasing CA concentrations. The nature of the collectors affects the morphology as well as packing of fibers. Fibers collected on paper have more uniform sizes, smooth surfaces, and fewer defects, whereas fibers collected on water are more varied in size. Electrically conductive solid collectors, such as Al foil and water, favor more tightly packed and less porous membranes. Porous collectors, like paper and copper mesh, produce highly porous membranes. The pores in membranes collected on the Al foil and paper are much better interconnected in the planar directions than those in membranes collected on water. There is evidence that electrospinning induces order in the fibers. Deacetylation of CA membranes is more efficient and complete in NaOH/ethanol than in aqueous NaOH, producing DS values between 0.15 and 2.33 without altering fiber surfaces, packing, or organization. The fully regenerated cellulose membranes are similarly hydrophilic as commodity cellulose fibrous matrices but absorb nearly 10 times as much water. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2119–2129, 2002     

Controlled grafting of MMA onto cellulose and cellulose acetate

Homogeneous graft copolymerization of methyl methacrylate onto cellulose and cellulose acetate was carried out in various solvents and solvent systems taking ceric ammonium nitrate, tin (II) 2-ethyl hexanoate [Sn(Oct)₂] and benzoyl peroxide as initiators. The effect of solvents, initiators, initiator and monomer concentration, on graft yield, grafting efficiency and total conversion of monomer to polymer were studied. Formation of Ce³⁺ ion during grafting in presence of CAN enhances the grafting efficiency. Methylene blue was used as a homopolymer inhibitor and controlled the molecular weight of the grafted polymer and its effect on grafting was also studied. In presence of MB, amount of PMMA homopolymer formation reduced and consequently grafting efficiency increased. The number average molecular weights and polydispersity indices of the grafted PMMA were found out by gel permeation chromatography. The products were characterized by FTIR and ¹H-NMR analyses and possible reaction mechanisms were deduced. Finally, thermal degradation of the grafted products was also studied by thermo-gravimetric and differential thermo-gravimetric analyses.     

4.2 Chemical characteristics of cellulose acetate

The chemical structure of cellulose acetates (CA), different synthesis paths, analysis strategies and the correlation of these structural features with properties, especially with the solubility are summarized. Alternative paths, in particular homogeneous procedures, for the synthesis of CA are described focusing on the application of new media and the in situ activation of acetic acid. The preparation of selectively substituted CA is reviewed including the defined hydrolysis under acidic or basic conditions. Strategies for the structure analysis by means of ¹H- and ¹³C-NMR spectroscopy and by means of chromatographic methods are discussed. In addition, the preparation and the application of a variety of mixed CA ethers and esters are described.     

Thermal stability of cellulose acetate urethanes

The thermal degradation of isocyanate modified cellulose acetate has been studied by dynamic thermogravimetric analysis in air. The activation energy of decomposition of these modified polymers has also been determined from differential thermal analysis thermograms. The data indicate that the cellulose acetate urethane polymers are thermally stable.     

The combined effect of wrinkles and noncircular shape of fibers on wetting behavior of electrospun cellulose acetate membranes

Roughness‐induced hydrophobicity is an area of rapid growth which can be achieved through surface texture or surface porosity. Characterizing the effect of surface roughness on wetting behavior of surfaces with irregular shapes has always been a challenging problem. In this work, changing the environmental conditions during electrospinning of hydrophilic cellulose acetate solutions produced highly porous ribbon like fibers, differed widely in their surface morphologies. All samples showed apparent hydrophobicity with water contact angles between 121° and 146°. The specific surface area was introduced for the first time, as a comprehensive parameter to predict contact angles of noncircular fibers. Statistical modeling revealed that the log‐linear models would better fit the data in comparison with the other linear forms. These results confirmed that the specific surface area could be an appropriate single variable for predicting the contact angles of multiscale porous and wrinkled structures of electrospun fibers. Moreover, the membrane produced at 20 °C temperature and the relative humidity of 60% revealed surprisingly high specific surface area (276.63 m²/g) that seems very promising for industrial applications such as separation technologies. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1012–1020     

Structure of swollen carboxylated cellulose fibers

Structural changes in cellulose fibers were elucidated for carboxymethylated fibers and fibers that are oxidized by periodate and chlorite. Non-fibrillated and partially fibrillated softwood, kraft fibers (SKF, m-SKF) were carboxymethylated to investigate the contribution of the S1 layer to the swollen fiber structures. Carboxymethylated non-fibrillated fibers (CMF) form balloon-like structures as they swell heterogeneously. When partially fibrillated SKF is carboxymethylated (m-CMF), the fibers do not exhibit this ballooning phenomenon due to the degradation of the S1 layer. Carboxymethylation disrupts the native cellulose crystalline structure without breaking the fibers apart. Periodate–chlorite oxidized fibers, on the other hand, swell homogeneously without disrupting the native cellulose I crystalline form. Periodate–chlorite oxidation damages all three secondary layers to the extent that any microfibril confinement caused by the swelling is removed. Each chemistry and mechanical treatment affects the cellulose fibers differently to yield various swollen structures.     

Electrokinetic properties of processed cellulose fibers

Natural cellulose fibers (cotton) comprise several noncellulose compounds (hemicellulose, wax and pectin substances) and cationic impurities which cause problems during different adsorption processes such as dying, or final fiber finishing and coating. Therefore the chemical purification (NaOH boiling, enzymatic purification, demineralization, extraction or oxidative bleaching) is the most important step in cellulose textile finishing. Alternative ways to describe the success of different processes in fiber purification which result in distinct surface charge and hydrophilicity are the determination of electrokinetic properties and the water uptake of textile fibers. The zeta-potential (ζ) was determined by streaming potential measurement as a function of the pH. From the ζ–pH functions the adsorption potential for all ionic species Φ_i (i.e. ( , in the case of potassium chloride solutions), the charge densities σ^k and the pK values are calculated according to the Börner and Jacobasch model.

The degradation and removal of hydrophobic noncellulose compounds which cover the primary hydroxyl and carboxyl groups of the cellulose polymer is clearly shown by an increase of the negative ζ of the plateau, which is in good agreement with the electrokinetic parameters of cotton samples determined by the Börner and Jacobasch model. The electrokinetic parameters determined by the Börner and Jacobasch model can be used to describe the adsorption/dissociation ability of textile fibers. The progress of the fiber processing (cleaning) is reflected by the surface charge as well as the hydrophilicity of the fiber.     

Electrostatically generated fibers of ethyl-cyanoethyl cellulose

Electrospinning was used to fabricate ethyl-cyanoethyl cellulose [(E-CE)C] fibers from tetrahydrofuran (THF) solutions. It was found that the solution jet is split or atomized during the flight to the grounded collector. Microcavities were detected on the surface of the fibers and these were attributed to the volatilization of the solvent (THF). The thinnest fibers generated had a diameter of about 250 nm. The crystallinity of the fibers varied with the voltage of the electrostatic field and it reached a maximum when the voltage of the electrostatic field was 50 kV.     

Microfibrillated cellulose/cellulose acetate composites: Effect of surface treatment

Microfibrillated cellulose (MFC), which consists of a web‐like array of cellulose fibrils having a diameter in the range of 10–100 nm, was incorporated into a cellulose acetate (CA) matrix to form a totally biobased structural composite. Untreated and a 3‐aminopropyltriethoxysilane (APS) surface treated MFC was combined with a CA matrix by film casting from an acetone suspension. The effectiveness of the surface treatment was determined by infrared spectroscopy and X‐ray photoelectron spectroscopy. The Young's moduli of APS treated MFC composite films increase with increasing MFC content from 1.9 GPa for the CA to 4.1 GPa at 7.5 wt % of MFC, which is more than doubled. The tensile strength of the composite film increases to a maximum of 63.5 MPa at 2.5 wt % compared to the CA which has a value of 38 MPa. The thermal stability of composites with treated MFC is also better than the untreated MFC. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 153–161, 2010     

Criteria of efficiency of cellulose acetate plasticization

Using cellulose acetate plastics as an example, it was shown that the search for the optimal concentrations of plasticizers should take into account the compatibility of components, as well as the thermophysical and mechanical properties of plasticized polymers. It was suggested that the temperature range of durability of a plastic, i.e., the difference between its glass-transition and brittle temperatures, be used as a plasticization efficiency criterion. Plasticizers that are well compatible with a polymer at processing temperatures but show a limited compatibility at its service temperatures make it possible to manufacture goods with an extended durable temperature range.     

FT Raman spectroscopic investigation of cellulose acetate

This study reports on a new method characterizing cellulose acetates and determining the contents of acetyl groups within cellulose acetates based on FT Raman spectroscopy. Cellulose acetates exhibiting diverse degrees of substitution ascribed to acetyl groups (DS_Ac) were obtained after the deacetylation of highly acetylated cellulose, i.e. cellulose diacetate and cellulose triacetate (CTA), with aqueous sodium hydroxide solution or 1,6-hexamethylenediamine (HMDA). After plotting the Raman intensity ratios between the bands at 1,740 and 1,380 cm⁻¹ against the DS_Ac, a calibration curve with high correlation coefficient of more than 0.99 was obtained. During the deacetylation of highly acetylated cellulose, a by-product—sodium acetate (NaOAc)—forms as the most possible salt among others. In order to determine the content of NaOAc, the mixtures of cellulose acetates and NaOAc were measured with FT Raman spectroscopy. Based on the relationship between the Raman intensity ratios as I₉₂₉/I₁₃₈₀ and the contents of NaOAc in the mixtures, a calibration curve exhibiting high correlation coefficient of more than 0.99 was generated.     

醋酸丁酸纤维素合成研究

以纤维素为原料,乙酐、正丁酸为酰化剂,浓硫酸为催化剂,合成了醋酸丁酸纤维素。FT-IR分析证实了酯化产物的生成。采用冰醋酸、NaOH、浓H2SO4、乙二胺等前处理方法对纤维素进行预处理,应用XRD和粘度法表征了产物的结晶结构和聚合度,结果表明冰醋酸处理法较好。适宜的合成条件为:纤维素10g、催化剂用量0.25mL、乙酐/正丁酸摩尔比1∶5、酯化反应温度70℃、酯化反应时间1h。