Water-soluble polymers as retention aids in a model papermaking system. III. Modified polyacrylamides

The pigment retention efficiency, in a model papermaking system, of anionically and cationically modified polyacrylamides was compared to that of the unmodified homopolymer. The anionic polyacrylamide is a much less efficient retention aid, especially at high pH's; the nonionic and cationic polymers perform similarly and without any marked pH dependence. However, it is the nonionic and anionic polyacrylamides which are similarly poor at fiber flocculation, at pH's between 4.5 and 7.5, whereas the cationic polymer is a good fiber flocculant. All three polymers stabilize pigment suspensions. The anionic polymer is not effective in heteroflocculation of mixed dispersions of fibers and pigment, whereas both the nonionic and cationic are good flocculants, the latter being less susceptible to overdosing. Equilibrium adsorption isotherms were determined; the cationic polymers is, unlike the other modified polyacrylamide, very well adsorbed by cellulose fibers. Onto titanium dioxide, polymers adsorbed in the order anionic < nonionic < cationic. A further differentiation of the cationic polymer is that it gives high pigment retention in sheet formation without markedly increasing the resistance to fluid flow through the forming sheet. Although a process of heteroflocculation is postulated for both nonionic and cationic polymers, in the former case it is thought that the primary adsorption is onto titanium dioxide, whereas with the latter it is onto cellulose.     

Electrokinetic properties of acrylic acid- and methacrylic acid-grafted polypropylene during chemically initiated graft copolymerization

Electrokinetic properties such as zeta potential (ζ), surface charge density (σ) and surface conductivity (K_s) of polypropylene fibers and those grafted with acrylic acid and methacrylic acid have been studied using the streaming potential method. At pH 7, the zeta potential of ?58.5 mV for control fibers reduced with increase in the amount of acrylic acid (16.2%) and methacrylic acid (28.2%) grafts to ?38.15 mV and ?38.30 mV, respectively. The drop in the negative zeta potential value is attributed to rendering polypropylene hydrophilic. The acrylic acid graft was found to be more effective than the equivalent amount of methacrylic acid graft in this respect due to the different chemical characters of the two graft copolymers. The negative zeta potential was also reduced to a considerable extent when cationic dye solution was streamed through the grafted polypropylene fibers, which is attributed to the deposition of dye cations on the negatively charged surface of the grafted fibers. The results on surface charge density and surface conductivity also indicated the hydrophilic character of grafted polypropylene.     

Preparation of grafted cationic polymer/silver chloride modified cellulose fibers and their antibacterial properties

In this article, we present a simple method for synthesizing antibacterial cellulose fibers that were modified with a cationic polymer and immobilized silver chloride (AgCl) particles. Relatively simple techniques of graft polymerization and onsite precipitation were used to fabricate the composites. Scanning electron microscopy images, Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, and energy‐dispersive X‐ray spectroscopy confirmed the immobilization of the AgCl particles. The observed inhibition zone of the immobilized AgCl particle composites indicated that the biocidal silver ions were released from the composites in aqueous solution. Compared with cationic‐polymer‐grafted cellulose fibers or AgCl alone, the cationic polymer/AgCl composites showed excellent antibacterial activity against Gram‐negative Escherichia coli and Gram‐positive Staphylococcus aureus. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42092.     

Interfacial properties of polyelectrolyte–cellulose systems. II. Electrokinetic properties of cellulose fibers with adsorbed monolayers of cationic polyelectrolyte

Zeta potential measurements by the streaming current method were performed on pulp (DP) fibers with or without irreversibly adsorbed monolayers of cationic polyelectrolyte. Factors affecting the electrokinetic properties of these fibers, such as the amount of adsorbed polymer, the polymer molecular weight (M_n 50,000 and 200,000), ionic strength (10^?5 ～ 10^?2M KCl), and the pH of the streaming medium (KCl solution), were examined. As the amount of adsorbed polymer increased, the negative zeta potential of the fibers decreased until the polarity of the zeta potential was reversed to the positive side. A marked change in the value of zeta potential was not observed when the formation of the saturated monolayer was completed. The zeta potential also varied in proportion to an increase in the amount of polymer adsorbed. Experimental results are interpreted with reference to the origin of the surface charge, the amphoteric nature of the surface, the modes of adsorption, and the adsorbed polymer chain configuration. Possible effects of the adsorbed monolayer formation on the structural change of the electric double layer at the fiber surface are discussed. It is concluded that the formation of a monolayer of cationic polyelectrolytes on the negatively charged cellulose fibers under the condition of k₁ > k₂ (part I) provides a means to arbitrarily control the charge of the fibers until formation of a saturated monolayer.     

Surface modification of natural substrates by atom transfer radical polymerization

Surface modification of various solid polysaccharide substrates was conducted by grafting methyl acrylate (MA) and styrene via atom transfer radical polymerization (ATRP) to produce well‐defined polymer grafts. The hydroxyl groups on the surfaces of the substrates were reacted with 2‐bromoisobutyryl bromide followed by graft copolymerization under ATRP conditions. The studied substrates were filter paper, microcrystalline cellulose, Lyocell fibers, dialysis tubing, and chitosan films. The modified substrates were analyzed by FT‐IR, water contact angle measurements, TGA, and SEM. FT‐IR characterization of the grafted substrates showed significant differences between the different substrates in the amount of grafted polymer. Higher amounts of polymer seem to be possible to graft from native cellulose substrates than from regenerated cellulose substrates. To investigate whether the grafted polymers were “living” after a longer time period, a second layer of polystyrene was grafted from a filter paper modified with PMA one year ago. FT‐IR characterization of the filter paper showed a peak corresponding to styrene, indicating that a block copolymer had been formed on the surface. Graft copolymerization can be used to change and tailor the surface properties of the polysaccharide substrates. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4155–4162, 2006     

Preparation and retention of poly(ethylene oxide)‐grafted cationic polyacrylamide microparticles

Novel microparticles of poly(ethylene oxide) (PEO)‐grafted cationic polyacrylamide were prepared through the free‐radical tetrapolymerization of acrylamide, acryloyloxyethyl trimethylammonium chloride (DAC), PEO macromonomer, and N,N′‐methylene bisacrylamide in an inverse microemulsion. The effects of the DAC content and the PEO chain length and content on the diameter and distribution of the microparticles were studied. Highly effective retention aids were obtained in retention experiments with fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 359–363, 2006     

Modified Polyethersulfone (PES) Ultrafiltration Membranes for Enhanced Filtration of Whey Proteins

Abstract

Application of membrane technology to whey protein separation is an interesting development that has seen growth in recent years. In particular, modification of existing membranes to impart charge properties on the membrane surface or in the pores has been shown to improve membrane selectivity, product purity, and throughput of protein solutions. This paper focuses on exploring the effects of membrane charge and solution pH on filtration of the major whey proteins α‐lactalbumin (14.1 kDa) and β‐lactoglobulin (18.4 kDa) using functionalized PES membranes. The membranes have an open pore structure containing charged sulfonated grafted polymer chains that allows for greater protein retention. The modified membranes were synthesized by polymerization of styrene in the membrane pores followed by sulfuric acid treatment of the resulting polystyrene grafts. The charged membrane gave a calculated selectivity of five times better than the raw membrane at pH 7.2 based on data from single protein transmission experiments. The enhanced selectivity of the tailor‐made membrane was due to increased retention of β‐lactoglobulin due to a reduction in molecular sieving combined with electrostatic repulsion between negatively charged β‐lactoglobulin and the negatively charged membrane.     

Enhanced wear resistance of ultra-high molecular weight polyethylene fibers by modified-graphite oxide

A simple and feasible method to enhance the wear resistance of ultra-high molecular weight polyethylene (UHMWPE) fibers was reported. The graphite oxide (GO) prepared using improved Hummer's method was surface modified with hexadecylamine to improve its compatibility with UHMWPE. Combined with well-dispersion of modified-GO (m-GO) in dichloromethane and the fact that the viscosity of UHMWPE suspension can be decreased by dichloromethane, the well dispersed m-GO/dichloromethane was added into UHMWPE suspension to improve m-GO dispersion in UHMWPE fibers. Finally, UHMWPE fibers with different m-GO concentration were prepared using gel spinning technology. The effect of m-GO concentration on the structure and properties of modified UHMWPE fibers were investigated. The results indicated that the melting temperature and crystallinity of m-GO modified UHMWPE fibers increased with increasing of m-GO concentration, while the fiber's crystal sizes and orientation increased, thus the tensile strength of m-GO modified UHMWPE fibers remained almost undamaged. The introduction of m-GO is beneficial to the formation of smooth transfer film on fiber's surface, which enhanced the self-lubrication of UHMWPE fibers. Compared with pure UHMWPE fiber, the UHMWPE fiber containing 1.5 wt% m-GO had enhanced wear resistance by 55.4% and still maintained high tensile strength of 29.98 cN dtex⁻¹.     

Cationic microparticle based flocculation and retention systems

Two types of microparticles, cationic silica particles (CSP) and cationic polymeric microparticles (CPMP), were used as flocculants and retention aids for solid suspensions in water and pulp, respectively. The solid suspensions used in this study include both positively and negatively charged precipitated calcium carbonate (PCC) and negatively charged polystyrene latex. It was found that CPMP was not an effective retention aid for positively charged PCC suspension in pulp if it was used alone. However, the retention of PCC was improved when negatively charged PCC was used. The combination of cationic microparticle systems (CPMP and CSP) with either cationically or anionically charged water-soluble polyacrylamides could significantly improve the flocculation and retention. The possible mechanisms of flocculation of solid suspensions with different dual-flocculant systems were discussed.     

Cationic latex interaction with pulp fibers. II. Modification of sheet properties by styrene butadiene latex with quaternized amino groups

Unbeaten kraft fibers covered with experimental cationic latexes were formed into sheets in which direct fiber-fiber bonds are replaced by polymeric bonds. The effect on sheet properties—breaking length, elongation at break, folding endurance, opacity, and light scattering—was evaluated as a function of latex composition. The composition was altered by either the ratios of styrene to butadiene in the polymer or by mixing soft film-forming and hard nonfilming latex. It is shown that, regardless of latex composition and mechanical properties of the polymeric film, all the latexes can modify the sheet properties to a similar extent, providing that the sheets are heated above the polymer's glass transition temperature. An improvement of tensile strength is accompanied by increased elongation. As a probable mechanism of reinforcement, it is suggested that the polymer acts as a filler of the fiber's surface irregularities, thus providing a larger contact area between fibers and an improved stress transfer between them.     

Water-soluble polymers as retention aids in a model papermaking system. I. Polyacrylamides

A series of polyacrylamides covering a wide molecular weight range were synthesized and employed as retention aids in a model papermaking system of cellulose fibers and titanium dioxide. The ability of the polymer to increase the proportion of added titanium dioxide that is retained in the formed paper sheet is strongly dependent on molecular weight, but not on pH. Adsorption isotherms on both pigment and fibers are strongly molecular weight dependent. Polyacrylamides have no more than a weak flocculating effect on fiber suspensions and stabilize dispersions of titanium dioxide. However, with mixed dispersions of fibers and pigment, in the same ratio (10:1) as in paper formation, strong coflocculation is evidenced by the higher molecular weight polyacrylamides. In this model system pigment retention is a consequence of a heteroflocculation by adsorbed polymer bridging between the particles of titanium dioxide and cellulose fibers, possibly augmented by improved filtration in the forming sheet. Electrostatic effects appear to be unimportant in the system under study.     

Improvement in adhesive‐free adhesion by the use of electrostatic interactions between polymer chains grafted onto polyethylene plates

The tensile shear adhesive‐free adhesion properties induced by electrostatic interactions between poly(acrylic acid) (PAA) and poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) chains grafted onto polyethylene (PE) with low‐density (LDPE) or high‐density (HDPE) plates were studied. PAA‐ or PDMAEMA‐grafted PE plates were immersed in a HCl or NaOH solution or water for 24 h, and their electrostatic properties were changed before they were overlapped with each other and heat‐pressed. The breaking of the substrate between the two plates with water‐swollen grafted layers was observed in the low range of grafted amounts in comparison with immersion in the acidic and basic solutions. The ability of the two plates with grafted polymer chains swollen in water to strongly bond with each other was a result of electrostatic interactions formed by positively charged PDMAEMA and negatively charged PAA chains. The breaking of the substrate in the case of adhesive‐free adhesion between quaternized PDMAEMA‐grafted and PAA‐grafted PE plates immersed in the basic solution occurred with lower grafted amounts of PAA. This came from the strong attractive force between dissociated anionic PAA chains and quaternized cationic PDMAEMA chains in the basic solution. In addition, the adhesive‐free adhesion strength of HDPE plates with the same grafted polymer chains encountered the breaking of the substrate with lower grafted amounts than that of LDPE plates. It was concluded that the grafting of polymer chains onto HDPE plates with high crystallinity was considerably restricted to the outer surface regions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2632–2638, 2006     

Polymer-grafted cellulose fibers. II. Polymer localization and induced alterations in fiber morphology

In methyl acrylate- or acrylonitrile-grafted northern softwood Kraft or southern softwood Kraft pulp fibers, polymer grafts are present almost homogeneously throughout the fiber wall, although some surface enhancement is observed. On unhydrolyzed fiber surfaces, acrylonitrile grafts protrude in clumps of tangled polymer tufts whereas methyl acrylate grafts form a more uniform, sometimes knobby surface coating. Grafting followed by hydrolysis causes extensive lengthwise splits in the S1 layer, which pulls away from the S2 layer. In the hydrolyzed solvent-dried fiber, the internal grafted polymer/cellulose domains create a unique filamentous and lamellar periodic substructure in the S2 wall. Coexisting with this substructure are numerous microvoids and occasional large pores. We believe that the enhanced absorbency of these fibers can be attributed to the S1 layer disruption, the presence of osmotically active polymer (sodium polyacrylate) incorporated extensively within the S2 wall, and the presence of a drastically altered, more accessible S2 wall substructure. Analytical electron microscopy is shown to be a useful technique for investigating polymer grafts in cellulose fibers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1471–1485, 1997     

Utilization of rice husk ash in green natural fiber-reinforced cement composites: Mitigating degradation of sisal fiber

This study aims to explore a novel approach to improve the durability of sisal fiber in cement composites by using by-products of biomass power plant: rice husk ash (RHA). The effects of two RHAs on the fiber's degradation were investigated indirectly by testing flexural behavior of sisal fiber-cement composite beams and directly by means of uniaxial tensile properties, thermal decomposition, crystallinity indices and microstructures of embedded fibers, after exploring up to 30 wetting and drying cycles. Allowing the distinction between pozzolanic activities, the efficiency of RHA was compared with two fly ashes and combinations of two clay minerals (metakaolin and nanoclay) with a cement substitution level of 30 wt.%. The durability of composites was improved considerably by incorporating RHA owing to the mitigation of fiber's degradation: the ultimate tensile strength and cellulose fraction of embedded fibers were improved by 384% and 45%, respectively. Fine RHA and the combination of metakaolin and nanoclay yield similar efficiency in mitigating degradation of sisal fiber, and are better than the coarse RHA and fly ashes. The correlations between cement hydration and sisal fiber degradation were analyzed. The results indicate that degree of hydration, calcium hydroxide content and alkalinity of the cement matrix play decisive roles in alkali attacks and mineralization of fiber's cell walls.     

Preparation and characterization of henequen cellulose grafted with methyl methacrylate and its application in composites

The grafting polymerization of methyl methacrylate (MMA) and cellulose from henequen (Agave fourcroydes) is investigated as a function of the initiator concentration (cerium-and-ammonium nitrate) and the monomer/cellulose ratio. The formation of cellulose-g-PMMA is confirmed by IR spectroscopy, DSC, and TGA. Both the initiator concentration and the MMA/cellulose ratio have a strong influence over the grafting parameters and over the molecular weight of the grafted PMMA. A higher initiator concentration and a lower monomer/cellulose ratio result in a lower molecular weight of the grafted polymer. Increasing the amount and the molecular weight of the grafted PMMA increases the compatibility of the fibers with SAN and PVC, as demonstrated by a mechanical test and scanning electron microscopy. SAN and PVC composites made with grafted cellulose exhibit higher flexural and tensile moduli, respectively, than those produced with the ungrafted fibers. Both moduli increase as the amount of reinforcement increases. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 339–346, 1997     

Fabrication of oriented electrospun cellulose nanocrystals–polystyrene composite fibers on a rotating drum

Nitrobenzene (CNC-1), trifluoromethyl benzene (CNC-2) modified and polystyrene-grafted (CNC-g) cellulose nanocrystals in polystyrene (PS)-N,N dimethylformamide (DMF) solutions were electrospun and collected as stretched and aligned fibers on a rotating drum. Scanning electron microscope pictures showed significant alignment in the case of unmodified and nitrobenzene-modified CNC-1/PS nanocomposite fibers once the linear speed of rotor reached to 15 m s⁻¹. Fiber diameter decrease was more strong with rotor speed increase in the case of trifluoromethyl benzene modified (CNC-2) and polystyrene-grafted (CNC-g) cellulose nanocrystals/PS systems. Dynamic mechanical analysis including storage and elastic modulus of electrospun-oriented fibers were performed on surface-modified and polymer-grafted CNC/PS samples. According to α transition peak, the increase in the glass-transition temperature with filler concentration was the highest in polymer-grafted CNC-g/PS composite fibers. It was due to the interpenetration of grafted polymer brushes and free polymer chains in continuous phase and resulted in restrictions of motions of polymer chains in the PS matrix. The elastic moduli of nitrobenzene (CNC-1) and trifluoromethyl benzene (CNC-2)-modified CNC-filled PS composite fibers agreed well with percolation model, which indicates the CNC–CNC interactions and network formation with an increase in concentration. Magnitude of the elastic modulus of polymer grafted CNC-g at 0.33 vol % in PS was significantly higher than the prediction from percolation theory. It was due the immobilized polymer chains around CNC-g particles. However, grafted polymer chains, at higher CNC concentrations acted like stickers among CNC particles and caused CNC agglomerates with entrapped free polystyrene from the matrix, thus caused a decrease in the elastic modulus. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48942.     

Blending chitosan-g-poly(caprolactone) with poly(caprolactone) by electrospinning to produce functional fiber mats for tissue engineering applications

Use of electrospun fiber mats for tissue engineering applications has become increasingly prominent. One of the most important polymers in research, poly(ε-caprolactone) (PCL), however, lacks biological performance, easy access to modifications and cellular recognition sites. To improve these properties and to enable further modifications, PCL was blended with chitosan grafted with PCL (CS-g-PCL) and subsequently processed via electrospinning. In this way, chitosan was enriched at the fiber's surface presenting cationic amino groups. The fiber mats were analyzed by various techniques such as scanning electron microscopy (SEM), confocal laser scanning microscopy (CLSM), and X-ray photoelectron spectroscopy (XPS). Furthermore, analyzing thermal properties and crystallinity, showed that an increased content of CS-g-PCL in blend composition leads to a higher overall crystallinity in produced fiber mats. Blending CS-g-PCL into PCL significantly increased initial cellular attachment and proliferation as well as cell vitality, while maintaining adequate mechanical properties, fiber diameter, and interstitial volume. As proof of principle for easy access to further modification, fluorescently labeled alginate (Alg-FA) was attached to the fiber's surface and verified by CLSM. Hence, blending CS-g-PCL with PCL can overcome an inherent weakness of PCL and create bioactive implants for tissue engineering applications. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48650.     

Preparation,characterization, and properties of cellulose–polyacrylamide graft copolymers

Graft copolymers of acrylamide on cellulose materials (α‐cellulose 55.8%, DP 287.3) obtained from Terminalia superba wood meal and its carboxymethylated derivative (DS 0.438) were prepared using a ceric ion initiator and batch polymerization and modified batch polymerization processes. The extent of graft polymer formation was measured in graft level, grafting efficiency, molecular weight of grafted polymer chains, frequency of grafting as a function of the polymerization medium, and initiator and monomer concentrations. It was found that the modified batch polymerization process yielded greater graft polymer formation and that graft copolymerization in aqueous alcohol medium resulted in enhanced levels of grafting and formation of many short grafted polymer chains. Viscosity measurements in aqueous solutions of carboxymethyl cellulose‐g‐polyacrylamide copolymer samples showed that interpositioning of polyacrylamide chains markedly increased the specific viscosity and resistance to biodegradation of the graft copolymers. The flocculation characteristics of the graft copolymers were determined with kaolin suspension. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 913–923, 2003     

Water‐soluble/dispersible cationic pressure‐sensitive adhesives. I. Adhesives from solution polymerization

Pressure‐sensitive adhesives (PSAs) have long been a problem as sticky contaminants for paper recycling mills. The main problem associated with such stickies is that the PSAs in the waste papers deposit on the felts, press rolls, and drying cylinders of paper machines, and this creates problems with paper formation, reducing the paper quality and paper machine runnability. The annual cost of stickies to the U.S. paper industry is estimated to be about $600,000,000–650,000,000. To solve this problem, a series of cationic water‐soluble/dispersible PSAs have been synthesized by the free‐radical solution polymerization of butyl acrylate and [3‐(methacryloylamino)propyl]trimethylammonium chloride in ethanol. The PSA end‐use properties, repulpability in paper recycling, and the effects on the properties of recycled paper products have been studied. The cationic PSAs can be dissolved or dispersed in water if the cationic charge density in the PSA backbone is controlled, and so they do not deposit as stickies during recycling and papermaking processes. Because the PSAs are cationically charged, they can easily be removed from the papermaking system by adsorption onto the negatively charged fibers and fine surfaces. Furthermore, the adsorbed colloidal or dissolved PSAs have little effect on the final paper properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1624–1630, 2003     

Water-soluble polymers as retention aids in a model papermaking system. II. Poly(vinylpyridines)

Three poly(4-vinylpyridines) and a poly(2-vinylpyridine) were studied for their effectiveness at increasing the retention of titanium dioxide a model papermaking system at pH 3.8. All the polymers are very efficient retention aids and do not greatly increase the time for the paper sheet to be formed. They are well adsorbed by both cellulose fibers and titanium dioxide. Although fiber suspensions are weakly flocculated by the poly(vinylpyridines), pigment suspensions are stabilized. Flocculation studies on mixed suspensions show that the poly(vinylpyridines) have a powerful heterocoagulation effect which mirrors the retention results. Some results are also reported in which the pH is brought to 6.5; under these conditions, polymer adsorption and its consequent effects compete with polymer precipitation.