Cellulose/casein blend membranes from NaOH/urea solution

Cellulose membranes and cellulose/casein blend membranes were successfully prepared from a new solvent system (6 wt % NaOH/4 wt % urea aqueous solution) by coagulation with a sulfuric acid aqueous solution. The structures and properties of the membranes were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), wide-angle X-ray diffraction, differential scanning calorimetry, and a tensile test. The experimental results showed that the suitable coagulation condition was 5 wt % H₂SO₄ for 5 min. When the casein content of the mixture was less than 15 wt %, the blend membranes were miscible because of the interactions between the hydroxyl groups of cellulose and the peptide bonds of casein. The blend membranes with 10 wt % casein had good miscibility, higher crystallinity, and the highest mechanical properties and thermal stability. In this case, the tensile strength and breaking elongation of the blend membranes were 109 MPa and 16%, respectively, and its pore size, obtained by SEM, was 290 nm, which suggests that the blend membranes provide a potential application for the field of separation technology. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3260–3267, 2001     

Morphology and properties of cellulose/chitin blends membranes from NaOH/thiourea aqueous solution

Blend membranes of chitin/cellulose from 12 : 50 to 12 : 250 were successfully prepared from cotton linters in 1.5M NaOH/0.65M thirourea solution system. Two coagulation systems were used to compare with each other, one coagulating by 5 wt % H₂SO₄ (system H), and the other by 5 wt % CaCl₂ and then 5 wt % H₂SO₄ (system C). The morphology, crystallinity, thermal stabilities, and mechanical properties of the blend membranes were investigated by electron scanning microscopy, atomic absorption spectrophotometer, infrared spectroscope, elemental analysis, X‐ray diffraction, different scanning calorimeter, and tensile tests. The cellulose/chitin blends exhibited a certain level of miscibility in the weight ratios tested. There were great differences between the two blends H coagulated with H₂SO₄ and C coagulated with CaCl₂ and H₂SO₄, respectively. The membranes H have a denser structure, higher thermal stability, tensile strength (σ_b), and crystallinity (χ_c), and values of σ_b (90 MPa for chitin/cellulose 12 : 150) were significantly superior to that of both chitin and regenerated cellulose membrane. However, the blend membranes C have much better breaking elongations (?) than that of membranes H, and relatively large pore size (2r_e = 210 μm), owing to the removal of a water‐soluble calcium complex of chitin as pore former from the membranes C. When the percentage content of chitin in the blends was from 5 to 7.5%, the values of breaking elongation for the blend membranes H and C all were higher than that of unblend membranes, respectively. The blends provide a promising way for application of chitin as a functional film or fiber in wet and dry states without derivates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2025–2032, 2002     

Synthesis and characterization of bacterial cellulose/alginate blend membranes

Bacterial cellulose and alginate in an aqueous NaOH/urea solution were used as substrate materials for the fabrication of a novel blend membrane. The blend solution was cast onto a Teflon plate, coagulated in a 5 wt % CaCl₂ aqueous solution, and then treated with a 1% HCl solution. Supercritical carbon dioxide drying was then applied for the formation of a nanoporous structure. The physical properties and morphology of the regenerated bacterial cellulose and blend membranes were characterized. The blend membrane with 80% bacterial cellulose/20 wt % alginate displayed a homogeneous structure and exhibited a better water adsorption capacity and water vapor transmission rate. However, the tensile strength and elongation at break of the film with a thickness of 0.09 mm slightly decreased to 3.38 MPa and 31.60%, respectively. The average pore size of the blend membrane was 10.60 Å with a 19.50 m²/g surface area. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cellulose acetate ultrafiltration membranes reinforced by cellulose nanocrystals: Preparation and characterization

Cellulose nanocrystals (CNCs) were used as a sustainable additive to improve the hydrophilicity, permeability, antifouling, and mechanical properties of blend membranes. Different CNC loadings (0–1.2 wt %) in cellulose acetate (CA) membranes were studied. The blend membranes were prepared by a phase‐inversion process, and their chemical structure and morphological properties were characterized by attenuated total reflectance–Fourier transform infrared spectroscopy, scanning electron microscopy, porosity, and mean pore size and contact angle measurement. The blend membranes became more porous and more interconnected after the addition of CNCs. The thickness of the top layer decreased and a few large holes in the porous substrate appeared with increasing CNC loading. In comparison with the pure CA membranes, the pure water flux of the blend membranes increased with increasing CNC loading. It reaches a maximum value of 76 L m^?2 h^?1 when the CNC loading was 0.5 wt %. The antifouling properties of the CA membrane were significantly improved after the addition of CNCs, and the flux recovery ratio value increased to 68% with the addition of 0.5 wt % CNCs. In comparison with that of the pure CA membranes, the tensile strength of the composite membranes increased by 47%. This study demonstrated the importance of using sustainable CNCs to achieve great improvements in the physical and chemical performance of CA ultrafiltration membranes and provided an efficient method for preparing high‐performance membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43946.     

Comparison of thermoset soy protein resin toughening by natural rubber and epoxidized natural rubber

Fully bio‐based soy protein isolate (SPI) resins were toughened using natural rubber (NR) and epoxidized natural rubber (ENR). Resin compositions containing up to 30 wt % NR or ENR were prepared and characterized for their physical, chemical and mechanical properties. Crosslinking between SPI and ENR was confirmed using ¹H‐NMR and ATR‐FTIR. All SPI/NR resins exhibited two distinctive drops in their modulus at glass transition temperature (T_g ) and degradation temperature (T_d ) at around ?50 and 215 °C, corresponding to major segmental motions of NR and SPI, respectively. SPI/ENR resins showed similar T_g and T_d transitions at slightly higher temperatures. For SPI/ENR specimens the increase in ENR content from 0 to 30 wt % showed major increase in T_g from ?23 to 13 °C as a result of crosslinking between SPI and ENR. The increase in ENR content from 0 to 30 wt % increased the fracture toughness from 0.13 to 1.02 MPa with minimum loss of tensile properties. The results indicated that ENR was not only more effective in toughening SPI than NR but the tensile properties of SPI/ENR were also significantly higher than the corresponding compositions of SPI/NR. SPI/ENR green resin with higher toughness could be used as fully biodegradable thermoset resin in many applications including green composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44665.     

Novel nanoporous membranes from regenerated bacterial cellulose

Bacterial cellulose (BC) in an NaOH/urea aqueous solution was used as a substrate material for thefabrication of a novel regenerated cellulose membrane. The dissolution of BC involved swelling BC in a 4 wt % NaOH/3 wt % urea solution followed by a freeze–thaw process. The BC solution was cast onto a Teflon plate, coagulated in a 5 wt % CaCl₂ aqueous solution, and then treated with a 1 wt % HCl solution. Supercritical carbon dioxide drying was then applied to the formation of a nanoporous structure. The physical properties and morphology of the regenerated bacterial cellulose (RBC) films were characterized. The tensile strength, elongation at break, and water absorption of the RBC membranes were 4.32 MPa, 35.20%, and 49.67%, respectively. The average pore size of the RBC membrane was 1.26 nm with a 17.57 m²/g surface area. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cellulose/chitin films blended in NaOH/urea aqueous solution

Regenerated cellulose/chitin blend films (RCCH) were satisfactorily prepared in 6 wt % NaOH/4 wt % urea aqueous solution by coagulating with 5 wt % CaCl₂ aqueous solution then treating with 1 wt % HCl. The structure, miscibility, and mechanical properties of the RCCH films were investigated by infrared, scanning electron microscopy, ultraviolet spectroscopies, X‐ray diffraction, tensile test, and differential scanning analysis. The results indicated that the blends were miscible when the content of chitin was lower than 40 wt %. Moreover, the RCCH blend film achieved the maximum tensile strength in both dry and wet states of 89.1 and 43.7 MPa, respectively, indicating that the tensile strength and water resistivity of the RCCH film containing 10–20 wt % chitin was slightly higher than that of the RC film unblended with chitin. Structural analysis indicated that strong interaction occurred between cellulose and chitin molecules caused by intermolecular hydrogen bonding. Compared to the mechanical properties of chitin film, those of the blend films containing 10–50 wt % chitin were significantly improved. This work provided a novel way to obtain directly chitin material blended in the aqueous solution. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1679–1683, 2002     

Preparation and characterization of soy protein isolate–carboxymethylated konjac glucomannan blend films

To improve the mechanical and water vapor barrier properties of soy protein films, the transparent films were prepared by blending 5 wt % soy protein isolate (SPI) alkaline water solution with 2 wt % carboxymethylated konjac glucomannan (CMKGM) aqueous solution and drying at 30 °C. The structure and properties of the blend films were studied by infrared spectroscopy, wide‐angle X‐ray diffraction spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential thermal analysis, and measurements of mechanical properties and water vapor transmission. The results demonstrated a strong interaction and good miscibility between SPI and CMKGM due to intermolecular hydrogen bonding. The thermostability and mechanical and water vapor barrier properties of blend films were greatly enhanced due to the strong intermolecular hydrogen bonding between SPI and CMKGM. The tensile strength and breaking elongation of blend films increased with the increase of CMKGM content: the maximum values achieved were 54.6 MPa and 37%, respectively, when the CMKGM content was 70 wt %. The water vapor transmission of blend films decreased with the increase of CMKGM content: the lowest value achieved was 74.8 mg · cm^?2 · d^?1 when the CMKGM content was 70 wt %. The SPI–CMKGM blend films provide promising applications to fresh food packaging. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1095–1099, 2003     

Theoretical studies on structural and electrical properties of PES/SPEEK blend nanofiltration membrane

Polyethersulfone (PES) nanofiltration membranes were prepared using a simple dry‐jet wet spinning technique with different contents of sulfonated poly(ether ether ketone) (SPEEK) ranging from 0 to 4 wt %. The structural parameters (r_p and A_k/Δx) and electrostatic properties (ξ and X) of the blend membranes were deduced by employing the combination of irreversible thermodynamic model, steric hindrance pore (SHP) model, and Teorell‐Meyer‐Sievers (TMS) model. The modeling results obtained have been analyzed and discussed. The mean pore radius and pore size distribution of the blends were also determined based on the theoretical models. The results showed that pore radius increased with increasing the concentration of SPEEK from 0 to 2 wt % but decreased with a further increase in SPEEK content. The water flux, however, showed a systematically increase with increasing SPEEK content. The SPEEK also showed significant effect on membrane electrical properties. Both effective charge density and ratio of effective charge density to electrolyte solution increased with increasing concentration of SPEEK in the dope solution, reaching a value of ?21.02 and ?2.29, respectively. The pore radius which was determined by using different transport models has also been analyzed and discussed. It is found that the addition of SPEEK into dope solution is one of the paramount parameters in developing the negatively charged nanofiltration membrane with enhanced water flux while retaining the pore radius in the nanometer range. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Porous poly(L‐lactic acid)/poly(ethylene glycol) blend films

Poly(L ‐lactic acid) (PLLA: M_w = 19.4 × 10⁴)/poly(ethylene glycol) (PEG: M_w = 400) blend films were formed by use of a solvent‐cast technique. The properties and structures of these blend films were investigated. The Young's modulus of the PLLA decreased from 1220 to 417 MPa with the addition of PEG 5 wt %, but the elongation at break increased from 19 to 126%. The melting point of PLLA linearly decreased with increases in the PEG content (i.e., pure PLLA: 172.5°C, PLLA/PEG = 60/40 wt %: 159.6°C). The PEG 20 wt % blend film had a porous structure. The pore diameter was 3–5 μm. The alkali hydrolysis rate of this blend film was accelerated due to its porous structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 965–970, 2004     

Blend membranes from carboxymethylated chitosan/alginate in aqueous solution

The blend membranes were satisfactorily prepared by coagulating a mixture of O‐carboxymethylated chitosan (CM‐chitosan) and alginate in aqueous solution with 5 wt % CaCl₂, and then by treating with 1 wt % HCl aqueous solution. Their structure and miscibility were characterized by scanning electron micrograph, X‐ray diffraction, infrared spectra, differential thermal analysis, and atomic absorption spectrophotometer. The results indicated that the blends were miscible, when the weight ratio of CM‐chitosan to alginate was in the range from 1 : 1 to 1 : 5. The polymers interpenetration including a Ca²⁺ crosslinked bridge occurred in the blend membrane, and leads to high separation factor for pervaporation separation of alcohol/water and low permeation. The tensile strength in the wet state (σ_b = 192 kg cm⁻² for CM‐chitosan/alginate 1 : 1) and thermostability of the blend membranes were significantly superior to that of alginic acid membrane, and cellulose/alginate blend membranes, owing to a strong electrostatic interaction caused by —NH₂ groups of CM‐chitosan with —COOH groups of algic acid. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 610–616, 2000     

Studies on cellulose acetate‐carboxylated polysulfone blend ultrafiltration membranes. III

Enhancement of the hydrophilicity in polymeric membrane materials results in membranes with higher flux and better membrane characteristics. Hence, polysulfone was carboxylated and ultrafiltration membranes were prepared from blends of cellulose acetate and carboxylated polysulfones having various degrees of carboxylation with a total polymer concentration of 20 wt % in casting solution and at different blend polymer compositions. The effects of degree of carboxylation on membrane characteristics such as compaction, pure water flux, and membrane hydraulic resistance (R_m) have been investigated. The influence of the polymer concentration in the blend solution on the performance of blend membranes at various blend polymer compositions has also been investigated and compared with that of blend membranes prepared from blends of cellulose acetate and polysulfone or carboxylated polysulfone with a total polymer concentration of 17.5 wt %. Further, the solute rejection performance of the membranes has also been investigated by subjecting the membranes to metal ion permeation studies using polyelectrolyte‐enhanced ultrafiltration. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 976–988, 2005     

羟乙基纤维素填充大豆蛋白塑料的结构和性能

将羟乙基纤维素(HEC)填充大豆分离蛋白(SPI)制备出生物可降解SPI/HEC复合材料(ES),并用X-射线衍射、差示扫描量热法、扫描电镜和拉力测试表征其结构和力学性能。值得关注的是,仅仅加入5%(wt)的HEC即可使复合材料的拉伸强度达到11.74MPa(比纯大豆分离蛋白材料增加了60%),同时其断裂伸长率增加了50%。HEC在共混材料内部因含量的增加,由单分子分散逐渐聚集形成独立的结晶微区,导致增强效果的降低和伸长率的明显下降。当HEC以单分子分散并通过其伸出的侧基嵌入基质时,较强的组分间相互作用实现了材料的同步增强增韧,是提高力学性能的最佳形式。     

Enhancement of the mechanical properties and thermostability of poly(vinyl alcohol) nanofibers by the incorporation of sodium chloride

The mechanical properties and thermostability of poly(vinyl alcohol) (PVA) nanofiber mats have been obviously improved by the incorporation of sodium chloride (NaCl). The tensile properties including tensile strength and modulus of membranes with an addition of 1.0 wt % NaCl increased from 2.51 to 4.22 MPa and 33.0 to 176.30 MPa, respectively, more than 160 and 700% of those of the electrospun pure PVA membranes. Moreover, thermogravimetric analysis showed that the initial decomposition temperature (T_i) and the half decomposing temperature (T_50%) of PVA nanofibers with the addition of NaCl were at least 26 and 59 °C higher than that of pure PVA nanofibers, respectively, indicating a strong interaction between the PVA and the salt ions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45981.     

Investigation on the effects of fabrication parameters on the structure and properties of surface‐modified membranes using response surface methodology

Surface Modifying Macromolecules (SMM) were used to alter the hydrophobicity of polyetherimide (PEI) hollow fiber membranes and the effects of three fabrication parameters, which are the mass fraction of PEI and SMM in the casting dope and air gap, on the properties of fabricated membranes were investigated by application of Response Surface Methodology (RSM). The fabricated membranes were characterized in terms of mean pore size (r_P,m), permeation rate of helium gas at 1 bar transmembrane pressure difference, membrane porosity, and contact angle of water with inner and outer surfaces of membrane. The regression models obtained for mean pore size and permeation rate have good statistical parameters and are accurate. The model for r_P,m predicts that plot of r_P,m versus air gap has a minimum point, whereas the plots of r_P,m versus PEI (wt %) and SMM (wt %) have maximum points. The regression model developed for membrane porosity predicts that membrane porosity decreases when air gap increases. Since water was used as bore fluid, the model developed for inner surface contact angle has low accuracy but the model developed for outer surface contact angle predicts that contact angle increases with SMM concentration in dope solution but there is a maximum point versus air gap. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Role of Star‐Like Hydroxylpropyl Lignin in Soy‐Protein Plastics

Summary: Star‐like hydroxypropyl lignin (HL) was compounded into soy protein isolated (SPI) to develop a potential biodegradable plastic with better mechanical performance than pure sheet‐SPI. The structure and properties of the composite materials were characterized by WAXD, DSC, SEM, TEM and tensile tests. The addition of just 2 wt.‐% HL resulted in tensile strength (σ_b) of 16.8 MPa, 2.3 times that of pure sheet‐SPI, with no accompanying decrease in elongation at break as a result of strong interaction and with good miscibility among components. As the HL content increased, the HL molecules could self‐aggregate as oblate supramolecular domains, while the stronger interactions between HL and glycerol resulted in the detaching of glycerol from the SPI matrix. It can be concluded that the insertion of HL as single molecules into the SPI matrix would provide materials with optimum mechanical properties. Compared with other lignin/SPI composites, the stretching chains on HL play a key role in the improvement of mechanical properties because of a stronger adhesion of HL onto the SPI matrix as well as the interpenetration of SPI into supramolecular HL domains.

Schematic illustration of the supramolecular domain created by the aggregation of hydroxypropyl lignin, which can interpenetrate with soy protein isolate.     

Synthesis,antimicrobial activity,and release of tetracycline hydrochloride loaded poly(vinyl alcohol)/soybean protein isolate/zirconium dioxide nanofibrous membranes

Tetracycline hydrochloride loaded poly(vinyl alcohol)/soybean protein isolate/zirconium (Tet–PVA/SPI/ZrO₂) nanofibrous membranes were fabricated via an electrospinning technique. The average diameter of the PVA/soybean protein isolate (SPI)/ZrO₂ nanofibers used as drug carriers increased with increasing ZrO₂ content, and the nanofibers were uneven and tended to stick together when the ZrO₂ content was above 15 wt %. The Tet–PVA/SPI/ZrO₂ nanofibers were similar in morphology when the loading dosage of the model drug tetracycline hydrochloride was below 6 wt %. The PVA, SPI, and ZrO₂ units were linked by hydrogen bonds in the hybrid networks, and the addition of ZrO₂ improved the thermostability of the polymer matrix. The Tet–PVA/SPI/ZrO₂ nanofibrous membranes exhibited good controlled drug‐release properties and antimicrobial activity against Staphylococcus aureus. The results of this study suggest that those nanofibrous membranes were suitable for drug delivery and wound dressing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40903.     

Morphological and structural formation of the regenerated cellulose membranes recovered from its cuprammonium solution using aqueous sulfuric acid

Morphological and structural formation of the regenerated cellulose membranes from its cuprammonium hydroxide solution by acid coagulation was investigated. Scanning electron microscopic observation revealed that the morphology of the membranes changed drastically as functions of both the cellulose concentration in the original cellulose solution C_Cell and the concentration of sulfuric acid as a coagulant C_H2SO4. It was found that at a constant polymer concentration (8 wt %) the membrane prepared by using 5 wt % aqueous sulfuric acid exhibits higher water flux, far smaller swelling anisotropy parameter L_t, and larger porosity P_r with a thinner skin structure, and these parameters were proven to be associated with lower (11 0) crystal plane orientation coefficient f_{∥(11 0)} compared with those for the membranes obtained by aqueous sulfuric acid with more than 10 wt %. On the other hand, at constant coagulant concentration (10 wt %) the membrane prepared by using the polymer solution with 5 wt % shows far greater P_r with practically no distinct skin structure; hence, a higher flux. The drastic changes in the morphology and structural parameters as functions of C_Cell and C_H2SO4 were found to be well correlated with abrupt changes in material transportation (copper ion, ammonium ion, and water) from the polymer solution to aqueous coagulants as a function of C_Cell and C_H2SO4. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1669–1678, 1999     

Hemodialysis membrane prepared from cellulose/N‐methylmorpholine‐N‐oxide solution. II. Comparative studies on the permeation characteristics of membranes prepared from N‐methylmorpholine‐N‐oxide and cuprammonium solutions

Two kinds of regenerated cellulose membranes for hemodialysis were prepared from casting solutions of N‐methylmorpholine‐N‐oxide (NMMO) and cuprammonium (denoted NMMO membranes and cuprammonium membranes, respectively). The concentration of cellulose in the casting solution investigated was 6–8 wt %. The permeation characteristics of both membrane series were compared in terms of the ultrafiltration rate (UFR) of pure water, the sieving coefficient (SC) of dextran, and the solute permeabilities of urea, creatinine, and vitamin B₁₂. The UFR and SC of the NMMO membranes were strongly affected by the cellulose concentration of the casting solution, and NMMO was a preferable solvent for the production of cellulose membranes with high performance; the cuprammonium solution gave low‐performance membranes. The pore structures of both types of membranes were estimated with the Hagen–Poiseuille law. The results showed that the NMMO membranes had larger pore radius and smaller pore numbers than the cuprammonium membranes. The differences in the membrane pore structures led to the differences in the performance between the two membrane series. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 333–339, 2003     

Effect of compatibility of cellulose acetate/poly(vinyl butyral) blends on pervaporation behavior of their membranes for methanol/methyl tert‐butyl ether mixture

Binary blends and their blend membranes of cellulose acetate (CA) and poly(vinyl butyral) (PVB) are prepared by solution blending. The compatibility of the blends is studied by viscometry and Fourier transform IR. It is found that the incompatibility of the blends is markedly manifested when the weight fraction of PVB in the CA/PVB blends (W_PVB) is located at higher regions. On the other hand, compatibility is obtained for the CA/PVB blends with lower W_PVB values, especially at about 0.2. This compatibility is believed to play a key role in the good pervaporation behavior of CA/PVB blend membranes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2434–2439, 2002