Effects of artificial weathering on the mechanical properties of paper‐based materials consolidated with polymeric materials

The study of polymer behavior over time represents the crucial stage in the setup of innovative methodologies for paper restoration. In this research, a series of laboratory simulations by accelerated aging and characterization tests by chemical and physical measurements were carried out on paper samples consolidated both by grafting polymerization with acrylic copolymers and by coating with waterborne polyurethanes with the aim of determining their harmlessness and long‐term effectiveness. In this way, our purpose was not only to verify possible risks for the paper materials but also to determine the advantages and potentialities of new restoration methods through an appropriate and essential working plan of investigations. From our evaluation, both the selected consolidation methods appeared unsuitable to be used in paper restoration because of the damage that they could cause on the paper materials because of their limited durability over time. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of nanosilica on the properties of polyester‐based polyurethane

Polyester‐based polyurethanes with embedded nanosilica particles were prepared. The viscosity of polyester resins without and with nanosilica was determined by rheoviscometry. The morphology and mechanical and optical properties of the polyurethane coatings were studied intensively with a transmission electron microscope, a pendulum hardness tester, a scanning probe microscope, an Instron testing machine, an abrader and an ultraviolet–visible spectrophotometer. The viscosity of the polyester resins increased as the nanosilica content increased. Nanosilica could basically be dispersed into the polyester and its polyurethane on a nanoscale. The addition of a small amount of nanosilica increased the hardness, abrasion resistance, and tensile properties of the polymer films. However, these mechanical properties could be worsened at higher nanosilica contents. The ultraviolet–visible spectra showed that the absorbance and reflection of ultraviolet–visible light by the polyurethane films increased as the nano‐SiO₂ content increased, especially at wavelengths of 290–400 nm. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 189–193, 2003     

Preparation and property of waterborne UV‐curable chain‐extended polyurethane surface sizing agent: Strengthening and waterproofing mechanism for cellulose fiber paper

Waterborne UV‐curable polyurethane (UWPU) dispersions with different hydrophilicity and functionalities were prepared by varying the content of dimethylol butanoic acid (DMBA) and pentaerythritol triacrylate (PETA). And linear and cyclic chain extenders with different functionalities were also incorporated into the UWPU backbone, including isophorone diamine (IPDA), diethylene triamine (DETA), and ethylene diamine (EDA). Effects of DMBA content, PETA content, photoinitiator content, UV curing time, chain extender on the properties of UWPU dispersions and films, as well as the properties of the unsized and sized paper were investigated. The water resistance and mechanical properties of sized paper were greatly relied on the particle size, the molecular weight, the croslinking density, and penetrability of UWPU. UWPU dispersion chain extended with IPDA (IPDA‐UWPU) displayed smaller particle size than that of UWPU. The paper sized with IPDA‐UWPU was endowed with best water resistance, tensile strength, folding strength and surface strength. XPS depth analysis revealed that IPDA‐UWPU exhibited better penetrability into the paper substrate than UWPU. SEM and AFM demonstrated that the smoothness of sized paper was improved, and the bond strength between fibers was enhanced. The obtained UWPU could be directly used as an effective and fast drying surface sizing agent for cellulose fiber paper. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42354.     

Effects of the reagent molar ratio on the phase separation and properties of waterborne polyurethane for application in a water‐based ink binder

Waterborne polyurethane (WPU) dispersions with a high solid content and low viscosity were prepared successfully by a two‐step polymerization with isophorone diisocyanate, poly(propylene glycol), and dimethylol propionic acid as the main raw materials. The molar ratio of hard segments to soft segments was controlled to investigate its influence on the particle size, particle morphology, stability of dispersions, and final properties of the WPU films. Measurements including attenuated total reflectance/Fourier transform infrared spectroscopy, transmission electron microscopy, differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction, polarizing optical microscopy, and contact angle tests were used to characterize the bulk structures, phase separation, thermal stability, crystallinity, and wettability of the WPU dispersions. The results indicate that all of the WPU dispersions with a high solid content (ca. 40 wt %) and low viscosity (ca. 20–50 mPa s) displayed excellent stability. The prepared WPU dispersions with acetone contents of 5–7 wt % could be used directly as an ink binder without removing the acetone; this is beneficial to industrial applications of water‐based ink binders. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45406.     

Structural variation in soft segment of waterborne polyurethane acrylate nanoemulsions

High solid content waterborne polyurethane acrylate (WPUA) nanoemulsions are prepared as textile finishes. Two structurally different soft segments, that is, polyether and polyester are used with isophorone diisocyanate, 2‐hydroxyethyl methacrylate, and butyl acrylate. Structural variations are investigated in features of nanoemulsions and their coatings. Physical properties of nanoemulsions, such as average particle size, stability, solid content, and viscosity, are investigated. Nanoemulsions with high solid content, that is, 40–47% are produced without any internal emulsifier. Average nanoparticle size, that is, <100 nm is confirmed by dynamic light scattering and atomic force microscopy (AFM). Fourier transform infrared spectroscopy proved synthesis of proposed WPUA products. Synergistic effect of polyurethane and acrylate is observed in chemical and water resistance of WPUA. Differential scanning calorimetry (DSC) and thermogravimetric analysis indicate stable uniformly cross‐linked network of WPUA. Application of nanoemulsions on 100% cotton fabric shows a significant improvement in tear strength, which is more pronounced for polyester‐based WPUA. Scanning electron microscope images of treated fabric samples show good adhesion of nanoemulsions on cotton surface. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41706.     

Biodegradable polyurethane materials from bark and starch. II. Coating material for controlled‐release fertilizer

Biodegradable polyurethane foams (PUFs) as coating materials for the controlled release of fertilizer were prepared from a four‐component system consisting of diisocyanate, polyester, Acacia mearnsi bark, and corn starch. Ammonium sulfate [(NH₄)₂SO₄] was used as a fertilizer to evaluate the effects of the preparation conditions on the release ratio. The release ratio of (NH₄)₂SO₄ decreased with an increasing amount of biomass in PUFs and increasing sizes of sample particles; the ratio increased with increasing doses of water, which was used as a foaming agent in the preparation of polyurethane, regardless of the amount of coating material. The remaining fertilizer in the polyurethane seemed to be released completely because the PUFs were degradable, to some extent, by soil microorganisms. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2948–2952, 2002     

Bamboo tar‐based polyurethane wood coatings

Bamboo tar is a natural resource of aromatic polyol obtained from a residue of by setting or distilling crude bamboo vinegar. In this study, the two‐packed polyurethane (PU) coatings were prepared by blending bamboo tar and castor oil varying with different weight ratios and polymeric toluene diisocyanate (PTDI) was used as a hardener at the NCO/OH molar ratio of 1.0. Six kinds of PU coatings were formulated and the viscosity, pot‐life, drying time, mechanical properties (hardness, tensile strength, impact resistance, adhesion, and abrasion resistance), gel content, durability, lightfastness, FTIR, thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA) were characterized. The results indicated that the bamboo tar containing PU film appearance is semitransparent yellow‐brown color and the wood texture could be kept after finishing. All PU films possessed excellent adhesion as well as durability. The increase in bamboo tar content led to shorten drying time of coatings and to increase in hardness, tensile strength, lightfastness, and thermal stability of films. From these results and due to a light smell flavor, it is suggested that the bamboo tar‐based PU coatings is suitable to be used as an exterior wood coatings. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical properties and biodegradability of crosslinked soy protein isolate/waterborne polyurethane composites

With anionic waterborne polyurethane (WPU) as a plasticizer and ethylene glycol diglycidyl ether (EGDE) as a crosslinker, we successfully prepared crosslinked soy protein isolate (SPI) plastics. Anionic WPU was mixed with SPI and EGDE in an aqueous dispersion at room temperature. The mixed aqueous dispersion was cast and cured, and the obtained material was pickled and hot‐pressed to produce the crosslinked SPI/WPU sheets. The resulting sheets containing about 60 wt % SPI were characterized with infrared spectroscopy, scanning electron microscopy, atomic force microscopy, dynamic mechanical analysis, and tensile testing, and biodegradation testing of the sheets was performed in a mineral salt medium containing microorganisms. The results revealed that the crosslinked SPI/WPU plastics with EGDE concentrations of 2–4 wt % possessed high miscibility, good mechanical properties, and water resistivity. In addition, the crosslinked sheets could be biodegraded, and the half‐life of the biodegradation for a sheet crosslinked with 3 wt % EGDE was calculated to be less than 1 month. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 465–473, 2005     

Preparation,morphology, and conductivity of waterborne,nanostructured, cationic polyurethane/polypyrrole conductive coatings

To endow cellulose fiber papers with good conductivity and simultaneously retain the mechanical strength of the conductive paper, a kind of waterborne, nanostructured, cationic polyurethane (CPU)/polypyrrole (PPy) conductive coatings were developed to modify the paper surface. Fourier transform infrared spectroscopy, atomic force microscopy, and thermogravimetry–differential thermogravimetry demonstrated that the peak associated with hydrogen bonding between ? NH and C?O of CPU was shifted, and chemical bonds between CPU and PPy were formed. Good compatibility between CPU and PPy was simultaneously established. Transmission electron microscopy and atomic force microscopy also suggested that PPy was encased and embedded in the CPU colloidal particles in a uniform style, and the surface of the CPU/PPy film was covered with a smooth, coherent conductive layer. With increasing pyrrole (Py) content from 5 to 20 wt %, the particle size increased from 55.08 to 74.59 nm, and the dispersity index (DPI) decreased. In addition, the conductivity of CPU/PPy increased from 0.1 to 5.0 S/cm. When the Py content was greater than 20 wt %, apparent increases in the particle size and DPI were detected as was particle coagulation; this resulted in decreased conductivity. Compared with the uncoated paper, the paper coated with CPU/PPy dispersions displayed different surface morphologies. The surface of the paper was completely enwrapped by the CPU/PPy conductive films when the coating amount was 45.42 g/m². With increasing coating amounts from 10.35 to 67.86 g/m², the conductivity of the conductive coated paper increased from 2.78 × 10^?3 to 2.16 S/cm, the tensile strength increased from 35.3 to 60.4 N m/g, and the conductive coated paper displayed good conductivity stability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41445.     

High‐performance waterborne coatings based on epoxy‐acrylic‐graft‐copolymer‐modified polyurethane dispersions

Polyurethane dispersions (PUDs) have been an active area of research since the early 1940s because of legislative restrictions on the use of organic solvents in conventional solvent‐based products and also because PUDs exhibit almost the same high performance levels as solvent‐borne polyurethanes. In the present study, properties of conventional waterborne PUDs are modified with epoxy‐acrylic graft copolymer blocks. The epoxy‐acrylic graft copolymers were first modified with ethylene diamine to give amine‐terminated blocks which in turn reacted with isocyanate‐terminated prepolymer (prepolymer mixing process) to give modified PUDs. Several experimental sets were prepared with varying compositions. The experimental sets were also prepared using conventional poly(ethylene glycol) blocks and ethylene diamine chain‐extenders. The physico‐chemical properties and film characteristics of the experimental sets show the dramatic improvement in important mechanical properties of PUDs due to grafting with epoxy‐acrylic copolymer blocks. Copyright © 2004 Society of Chemical Industry     

Performance of palm oil‐based dihydroxystearic acid as ionizable molecule in waterborne polyurethane dispersions

Waterborne polyurethane dispersions (WPUDs) containing a renewable palm oil‐based 9,10‐dihydroxystearic acid (DHSA) as an isocyanate‐reactive compound bearing ionizable carboxylic group to incorporate hydrophilic groups into the polymer chain have been successfully prepared. The WPUDs were prepared by using polyether and polyester polyols of 2000 molecular weight, DHSA and its traditional petroleum‐based counterpart 2,2‐bis(hydroxymethyl)‐propionic acid (DMPA), and an aliphatic diisocyanate (isophorone diisocyanate, IPDI). A comparison was made between the properties of WPUDs obtained using blends of DHSA and DMPA at different molar ratios and a reference WPUD based on DMPA. The particle size of polyester type WPUDs containing DHSA was reduced at a 0.5 to 0.5 molar ratio of DMPA to DHSA. A lower initial temperature was used in the preparation of NCO‐prepolymers with DHSA as compared to DMPA and this eased the preparation of WPUDs. The effect of molar ratio of DMPA to DHSA on the properties of films and coatings prepared with WPUDs was evaluated. The best properties were obtained with WPUDs prepared with a 0.5 to 0.5 molar ratio of DMPA to DHSA. The incorporation of renewable palm oil‐based DHSA into WPUDs improved water resistance (lower water uptake) and exhibited good combination of properties including hardness, adhesion strength, tensile strength, and elasticity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43614.     

Effect of oleic acid content and chemical crosslinking on the properties of palm oil‐based polyurethane coatings

Polyurethanes (PU) were prepared by reacting palm oil‐based polyols and aromatic diisocyanate (toluene 2, 4 diisocyanates). The content of oleic acid was varied in the polyester polyols and the hydroxyl value was fixed to be 140 mg KOH g^?1. The NCO/OH ratios were varied to 1.2, 1.4, and 1.6. Crosslinking density of the PU was measured by swelling in toluene at room temperature. It was found that the crosslinking increased with decreasing oleic acid content and increasing NCO/OH ratio. The samples were assessed by thermogravimetric analysis, differential scanning calorimetric, and short‐term creep measurements. The highest rupture strength of the PU films was 36 MPa and thermostability improved as the oleic acid content and the NCO/OH ratios were increased in the sample. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of aqueous polyurethane dispersions with well‐defined soft segments

Novel aqueous polyurethane (PU) hybrid dispersions were successfully prepared with 5–15 mol % functionalized hexamethylene diisocynate trimer modified by N‐(n‐butyl)‐3‐aminopropyltriethoxysilane and dihydroxylpropyl‐terminated siloxane oligomers (TS). The results of the differential scanning calorimetry and X‐ray diffraction tests show that the degree of segment order was reduced by the introduction of TS. The hybrid polymer films with TS introduced into the PU backbone displayed excellent water and xylene resistance. Atomic force microscopy showed that the films had a smooth surface. It was noticeable that the tensile strength (σ_b) and Young's modulus of the films increased simultaneously when TS was incorporated into PU; σ_b of the PU15 film with 15 mol % TS was much higher than that of the neat PU0 film, and the breaking elongation of the film with 10 mol % TS was clearly higher than that of the other films. The results indicate that an appropriate content of TS significantly improved the properties of the aqueous PU hybrids. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallinity evolution of soft segments during the synthesis of polyester‐based waterborne polyurethane

Polyester‐based waterborne polyurethane (WPU) dispersions having poly(ethylene glycol) adipate diol, isophorone diisocyanate, and hexamethylene diisocyanate as the main raw materials were synthesized by an acetone process. In each step of the synthesis process, the intermediate products were collected, and the crystallization morphologies and relative crystallinity (X) of the soft segments (SSs) in their films were investigated by means of polarizing optical microscopy, differential scanning calorimetry, and X‐ray diffraction. The fracture surfaces and thermostability of the intermediate films were also investigated by scanning electron microscopy (SEM) and TGA, respectively. The results show that the crystalline dimensions of the SSs decreased substantially during the synthesis process of WPU. X of the SSs decreased after the prepolymerization reaction and increased after the hydrophilic chain‐extending reaction, then decreased after emulsification, and finally increased after the secondary chain‐extending reaction. Moreover, The SEM photos indicate that with decreasing crystalline dimensions, the fracture mechanisms of the intermediate films varied gradually from brittle failure to ductile fracture. The thermostability of the intermediates obtained in each step of the synthesis process was in accordance with the variation tendency of the X of the SSs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40270.     

Oil‐absorbent polyurethane sponge coated with KH‐570‐modified graphene

Polyurethane (PU) sponge has become a preferred oil adsorbent in recent oil‐spill accidents. To make the sponge superhydrophobic and superoleophilic, this study used graphene (GN), which was modified with γ‐methacryloxypropyl trimethoxy silane (KH‐570), to coat the PU sponge (called the KH–GN sponge). This study showed the best loading capacity (11.96%) of the KH‐570‐modified GN on the sponge. The contact angles of the KH–GN PU sponge were 161° for water and 0° for soybean, diesel, and pumping oil. It had good selectivity for oil over water, and the KH–GN sponge achieved adsorption equilibrium within a few seconds. The absorption capability of the KH–GN sponge was up to 39 times greater. Additionally, the KH–GN PU sponge could be reused for oil–water separation for more than 120 cycles without losing its superhydrophobic and superoleophilic properties. Therefore, the sponge prepared in this study could be a desirable material for the cleanup of oil spills. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41821.     

New intumescent flame‐retardant agent: Application to polyurethane coatings

The first part of this investigation focused on the synthesis and characterization of a new type of intumescent flame‐retardant (IFR) agent. Four steps were used in the synthesis process. The structure was characterized by FTIR, magic‐angle spinning nuclear magnetic resonance (MAS‐NMR) ¹³C spectroscopy, and elemental analysis. The addition of an IFR agent into polyurethane (PU) varnish led to an improvement in its carbonization and flame‐retardant (FR) properties. The second part focused on the evaluation of such characteristics as FR property, thermal stability of IFR/PU‐based coatings, rheology of IFR/PU‐based coating solutions, and mechanical properties such as hardness, adhesion, and flexibility of IFR/PU‐based dry coating films. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1193–1206, 2004     

Dry‐peelable temporary protective coatings from waterborne self‐crosslinkable sulfourethane–silanol dispersions

Novel temporary protective coatings were prepared by the addition of release additives to waterborne polyurethane dispersions. New types of self‐crosslinkable sulfourethane–silanol (SUS) dispersions were utilized as the peelable coatings. These dispersions are stable, low‐volatility organic chemical (VOC) waterborne dispersions that spontaneously crosslink upon drying without extra additives or processing steps. Tensile strengths up to 6000 psi with elongations between 300–600% were obtained for the crosslinked films. The adhesion of the films to a variety of substrates can be controlled by the addition of hydrophilic additives, including glycerol, oligomers of glycerol, and poly(ethylene glycol) derivatives. Alternatively, hydrophobic additives that are water dispersible, such as paraffin waxes and sulfated castor oil, can also be used to control adhesion. In addition, this technique can be utilized for the release of films derived from a wide variety of waterborne urethane dispersions, including carboxylated polyurethane ureas. The removable coatings are useful for the temporary protection of plastic surfaces during thermoforming processes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1443–1449, 2004     

Antiwear and lubrication properties of polyurethane/polytetrafluoroethylene‐bonded coating

Polytetrafluoroethylene (PTFE) particles were irradiated with ⁶⁰Co γ‐ray to improve their dispersing capacity in polyurethane (PU), which was used as a binder of a PTFE‐based bonded solid lubricating coating. The PU/PTFE‐bonded solid lubricating coating was prepared on a steel block by spraying and curing at room ambient, and the tribological properties of the PU/PTFE coatings were evaluated on a ring‐on‐block tester at a speed of 1.25–2.5 m/s and a load of 314–785 N. The wear life of bonded coatings on PTFE volume concentrations, curing humidities and times, coating thickness, and sliding conditions was also investigated. It was found that a 60‐μm thickness coating, which has a 40% PTFE volume concentration, cured at 75% relative humidity for 4 days, has a longer wear life of 844 m/μm at 314 N and 1.25 m/s. The PTFE/PU coating was wear‐resistant when the load × speed value was less than 687 Nm/s^?1; at same time, the wear life for a thinner coating is sensitive to sliding condition variations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3454–3459, 2002     

Degradation of polyurethane coating materials from liquefied wheat straw for controlled release fertilizers

Polyurethane (PU) was synthesized by liquefied wheat straw and isocyanates for controlled release fertilizers (CRFs). CRFs coated by PU were buried in soil for 12 months. The degradation degree and mechanism of PU coating materials were observed by thermogravimetric analysis (TGA), Atomic Force Microscope (AFM), differential scanning calorimetry (DSC), X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and Fourier transform infra‐red spectroscopy (FTIR). Significant microscopic morphology of PU exhibited many small chips or stereovision holes caused by biodegradation or hydrolytic degradation due to the presence of natural polymer wheat straw. AFM results depicted the plane and height topography changes of PU before and after 12 months burial time, showing the swelling morphology of buried PU. TGA and FTIR results confirmed the disintegration of PU polymer due to the presence of isocyanates monomers in the PU12. XPS revealed an accumulation of biofilm on the surface of buried PU, providing the evidence of biodegradation mechanism. Pot experiment indicated the resin residual coating has a positive effect on soil quality. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44021.     

Effect of the synthesis route on the structure and properties of polyurethane/nitrokonjac glucomannan semi‐interpenetrating polymer networks

With a synthesis route differing from previous methods, novel semi‐interpenetrating polymer networks (semi‐IPNs), coded UNK‐II, were synthesized by the initial mixing of nitrokonjac glucomannan (NKGM) with castor oil in butanone and the subsequent addition of toluene diisocyanate (TDI) to begin the polymerization reaction in the presence of 1,4‐butanediol (BD) as a chain extender at 60°C. The results from dynamic mechanical analysis, differential scanning calorimetry, and ultraviolet spectroscopy indicated that a certain degree of microphase separation occurred between soft and hard segments of polyurethane (PU) in the UNK‐II sheets. The α‐transition temperature, glass‐transition temperature, heating capacity, and tensile strength increased with an increase in the NKGM content, and this suggested an interaction between PU and NKGM in the UNK‐II sheets. In a previous method, semi‐IPN materials (PUNK) were synthesized by the polymerization reaction between castor oil and TDI, and then this PU prepolymer was mixed with NKGM and cured in the presence of BD as a chain extender. The PUNK sheets had relatively good miscibility and mechanical properties. However, for UNK‐II sheets prepared by the method reported in this work, NKGM mainly played a role in reinforcement. When the NKGM content was less than 10%, the UNK‐II sheets exhibited good miscibility, tensile strength (26–28 MPa), and breaking elongation (130–140%), similar to those of PUNK materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1948–1954, 2003