Hydrolyzed soy protein isolates modified urea–formaldehyde resins as adhesives and its biodegradability

The hydrolytes soy protein isolates (HSPI)-modified urea–formaldehyde (UF) resins were synthesized via copolymerization process. The best bonding strength is 1.50 MPa and improves 51.5% compared with pure UF. In addition, the formaldehyde emission decreased. The effect of (HSPI) on the biodegradable (UF) resins was investigated. Biodegradation was evaluated by composting under controlled conditions in accordance with ISO 14855. The faster degradation rate was obtained when lower hydrolysis degree of HSPI was added into the system. Characterization of the resulting samples was performed by attenuated total reflection Fourier transform infrared spectroscopy, thermo-gravimetric analysis, XRD, scanning electron microscopy, and AFM. The results showed that no evidence of biodegradation was found for UF resins. The UF modified with lower hydrolysis degree of hydrolytes soy protein isolates (HSPI) resulted in a faster degradation rate. The HSPI in the network of modified UF degraded first, which resulted in the broken of the network of HSPI-modified UF resins. The thermal stability of degraded resins was found to be enhanced as the mineralization time increased. Not only the surface of the sample was degraded, but also the crystalline regions of the samples were also decomposed. The degradation on the modified UF surface occurs mainly via the formation of holes. The roughness of the degraded surfaces of modified UF resins increases with the hydrolysis degree of HSPI decreases. The presence of HSPI has driven the degradation of urea–formaldehyde. The modified resins used as adhesives in biodegradable seedling container can be seen as a controlled release source of nitrogen fertilizer.     

The effect of the heat treatment of spruce wood on the curing of melamine–urea–formaldehyde and polyurethane adhesives

The effect of the heat treatment of spruce wood on the curing of melamine–urea–formaldehyde (MUF) and polyurethane (PUR) adhesives was monitored by measuring their rheological properties by means of a rheometer. Instead of the standard aluminium discs, wooden discs, made from heat-treated wood with different degrees of thermal modification and conditioned in different climates, were used. The wooden discs provided more realistic curing of the adhesives compared to the real-life bonding of wood, because of solvent absorption. The results of the rheological measurements suggested that the modified wood inhibited the curing of MUF and PUR adhesives. The curing of the MUF adhesive was slower because of the reduced absorption of water from the adhesive. The curing of the one-component PUR adhesive was affected by the lower moisture content (MC) of the modified wood.     

Preparation and performance of lignin–phenol–formaldehyde adhesives

Steam explosion lignin phenol formaldehyde (SEL–PF) adhesives were prepared by ternary gradual copolymerization. The parameters for the phenolate of steam explosion lignin (SEL) and preparation of SEL–PF adhesives were optimized. Under the optimum phenolate conditions, the phenolic hydroxyl content of lignin increased by 130%, whilst the methoxyl content was reduced by 68%. The SEL–PF adhesives were used to prepare plywoods by hot-pressing. The pH value, viscosity, solid content, free phenol content and free formaldehyde content of SEL–PF adhesives were investigated. The bonding strengths of the plywoods glued with SEL–PF adhesives were determined. The maximum SEL replacement percentage of phenol reached 70 wt%, and the properties of adhesives and plywoods met the Chinese National Standard (GB/T 14732-2006) for first grade plywood.     

13C NMR study on the structure of ZnO-catalyzed phenol–urea–formaldehyde resin during its synthesis process

The structure of ZnO-catalyzed phenol–urea–formaldehyde (PUF) resin at different synthesis stages was analyzed by liquid ¹³C nuclear magnetic resonance spectroscopy. The results showed that the general structure of ZnO-catalyzed PUF resin was almost the same as the control PUF resin. Addition reaction between phenol and formaldehyde mainly occurred at the first stage. Total methylol groups amount between phenols of the control resin was a little lower than that of the ZnO-catalyzed PUF resin. Co-condensation and self-condensation reaction occurred at the second stage. The preparation method of ZnO-catalyzed PUF resin favored the co-condensation reaction between phenol methylol groups and urea units, while self-condensation reaction dominated the control resin at the second stage. Formaldehyde completely reacted for both the control and ZnO-catalyzed PUF final resin. The total amount of methylol and methylene groups between urea units and phenols, respectively, was almost the same for the two final resins. The total quantity of methylol groups between phenols represented a continuing downward trend from the first stage to the final stage, and the amount of methylol group (p-Ph–CH₂OH) of ZnO-catalyzed PUF resin was 30% more than that of the control resin. Total co-condensed methylene groups amount of ZnO-catalyzed PUF resin was greater than that of the control resin, which indicated that ZnO could make the urea units well incorporated into the co-condensed PUF resin.     

The effect of soda bagasse lignin modified by ionic liquids on properties of the urea–formaldehyde resin as a wood adhesive

The aim of this research was to investigate the influence of lignin modified by ionic liquids on physical and mechanical properties of plywood panels bonded with the urea–formaldehyde (UF) resin. For this purpose, soda bagasse lignin was modified by the 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) ionic liquid and then the various contents of unmodified and modified lignins (10, 15, and 20%) were added at pH=7 instead of second urea during the UF resin synthesis. The physicochemical properties of the prepared resins as well as the water absorption, shear strength, and formaldehyde emission of the plywood panels made with these adhesives were measured according to standard methods. According to Fourier Transform Infrared (FTIR) Spectrometry, by treatment of lignin, the C=O, C–C, and C–H bonds decrease while the content of the C–N bond dramatically increases. Based on the finding of this research, the performance of soda bagasse lignin in UF resins dramatically improves by modification by ILs; as the resins with modified lignin yielded lower formaldehyde emission and water absorption when compared to those made from unmodified lignin and commercial UF adhesives, respectively. The shear strength as well as wood failure percentages are lower for the panels produced with modified lignin than for the panels produced with UF resins alone.     

Effect of alkalinity on the structure of phenol–formaldehyde resol resins

Two phenol–formaldehyde resol resin series with different methylation- and condensation-stage alkalinities were studied. The first series was impregnation resins having a methylation alkalinity between 0.5 and 1.5 wt % and a condensation alkalinity of 1.5 wt %. The second series was adhesive resins with a methylation alkalinity between 0.5 and 3.5 wt % and a condensation alkalinity of 6.0 wt %. The chemical structure was analyzed by ¹³C-NMR spectroscopy, and reactivity, by differential scanning calorimetry (DSC). The methylation alkalinity was found to affect the distribution of the structural groups of both phenol–formaldehyde impregnation and adhesive resins, but not to the same extent as did the total condensation alkalinity. Also, the results of the DSC analysis illustrate best the reactivity differences due to the condensation alkalinity. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 258–262, 2001     

Effect of spent sulfite liquor on urea–formaldehyde resin performance

Combination of urea–formaldehyde (UF) resins with technical lignins has been often reported in the literature. However, the actual implications of this approach have not been effectively addressed yet. In this work, unmodified thick spent sulfite liquor (TSSL) and hydroxymethylated TSSL (TSSLH) were incorporated in a standard UF resin in different amounts (10 and 20%) and at different stages. When 10% of TSSLH was incorporated after the synthesis, the produced particleboards performed equivalently to when 90% of UF resin was used. In all other cases tested, combining UF resin with TSSL/TSSLH actually led to lower internal bond strengths. The results evidence that addition of TSSL or TSSLH does not have a beneficial effect on UF bonding performance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47389.     

The effect of the change of the structure on oxidative dehydrogenation of propane over cerium–zirconium catalysts

A series of pure CeO₂, ZrO₂, and CeZrO_x mixed metal oxide catalysts were prepared by a wetness impregnation method and were applied to the dehydrogenation of propane to propylene at 500°C and 0.1 MPa. The prepared catalysts were characterized by thermal gravimetric analysis (TGA), Brunauer, Emmett, and Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopes (TEM), Raman spectroscopy, and H₂-TPR. It was observed that the zirconium content of the solid solution of the mixed metal oxide catalyst was 5%–25%, while the zirconium content of the material with phase segregation was higher (50%). The addition of zirconium was proven to decrease the oxygen vacancy concentration on the catalyst surface and change the intensity of (111) crystal of cerium oxide in the catalysts. Among the prepared catalysts, the Ce_0.90Zr_0.10O_x catalyst with the maximum strength of the (111) crystal plane of cerium oxide exhibited the better catalytic oxidation performance for the dehydrogenation of propane to propylene. Compared with ZrO₂ in the blank experiment, the average propane conversion and propylene selectivity of the Ce_0.90Zr_0.10O_x catalyst were increased by 10.78% and 17.95%, respectively.     

Effect of emulsifier on poly(urea–formaldehyde) microencapsulation of tetrachloroethylene

Microcapsules containing tetrachloroethylene as an internal phase were prepared by in situ polymerization of urea–formaldehyde (UF) without prepolymerization. The effects of different emulsifiers on the process of microencapsulation and morphology of microcapsules were investigated. The results show that the emulsifier gum arabic (GA) can effectively slow down the deposition rate of resin onto the oil/water interface, which can lead to smooth and compact surface of microcapsules. The surface activity of GA was also enhanced by complex formation of gum arabic and sodium dodecyl benzene sulfonate. The microcapsules represent good thermal and barrier property as a result of the formation of capsule wall with compact microstructure.     

Nano porous structure of resorcinol–formaldehyde xerogels and aerogels: effect of sodium dodecylbenzene sulfonate

In the past two decades, resorcinol?Cformaldehyde (RF) gels have found widespread applications owing to their low density and adjustable pore size. They are usually prepared through sol?Cgel polymerization of the monomers in an aqueous media followed by evaporative or supercritical drying. In this study, RF gels were synthesized via sol?Cgel polymerization in the presence of sodium dodecylbenzene sulfonate (NaDBS) followed by ambient and supercritical drying. Dimensional measurements along with N₂ sorption analysis and Scanning electron microscopy (SEM) micrographs revealed that pore structure of the gel is chiefly affected by NaDBS. In all samples (xerogels and aerogels), maximum densities were observed at a critical NaDBS concentration (~1?w/v%), whereas considerable pore size increments and pore size distribution broadenings were found at higher concentrations of NaDBS (??5?w/v%). The most increased mesopore volumes were detected in xerogels (133% for acetone-dried and 67% for water-dried samples), while concerning aerogels, the pore sizes enlargement to macropore regime was observed at 5?w/v% of NaDBS. SEM micrographs, in agreement with porosity analysis, depicted that very large pore volumes could be obtained when supercritical drying was employed. However, in the case of xerogels, a more dense structure with smaller pores (micro and mesopores) exists which can only be altered slightly when using large amounts of NaDBS. The results showed that the RF gel pore texture, independent of drying technique, was strongly influenced by the addition of NaDBS, which should be taken into account when using this surfactant in the gel formulation for a wide variety of applications.     

Influence of nanoclay on urea–glyoxalated lignin–formaldehyde resins for wood adhesive

In this research, the influence of nanoclay on urea–glyoxalated lignin–formaldehyde (GLUF) resin properties has been investigated. To prepare the GLUF resin, glyoxalated soda baggase lignin (15 wt%) was added as an alternative for the second urea during the UF resin synthesis. The prepared GLUF resin was mixed with the 0.5%, 1%, and 1.5% nanoclay by mechanically stirring for 5 min at room temperature. The physicochemical properties of the prepared resins were measured according to standard methods. Then the resins were used in particleboard production and the physical and mechanical properties of the manufactured panels were determined. Finally, from the results obtained, the best prepared resin was selected and its properties were analyzed by differential scanning calorimetry (DSC), Fourier transform infrared spectrometry (FTIR), and X-ray diffractometry (XRD). Generally the results indicated that the addition of sodium-montmorillonite (NaMMT) up to 1.5% appears to improve the performance of GLUF resins in particleboards. The results also showed that nanoclays improved mechanical strength (modulus of elasticity (MOE), Modulus of Rupture (MOR), and internal bond (IB) strength) of the panels bonded with GLUF resins. The panels containing GLUF resin and nanoclay yielded lower formaldehyde emission as well as water absorption content than those made from the neat GLUF resins. XRD characterization indicated that NaMMT only intercalated when mixed with GLUF resin. Based on DSC results, the addition of NaMMT could accelerate the curing of GLUF resins. The enthalpy of the cure reaction (ΔH) of GLUF resin containing NaMMT was increased compared with neat GLUF resin. Also the results of FTIR analysis indicated that addition of NaMMT change the GLUF resins structures.     

The effect of catalyst and heat treatment on the properties of carbon–metal composites

Carbon gel and carbon–nickel–palladium doped gels (C–Ni–Pd) were prepared by carbonising resorcinol–formaldehyde (RF) hydrogel and resorcinol–formaldehyde–nickel–palladium (RF–Ni–Pd) hydrogels at 900 °C in a nitrogen atmosphere. RF and RF–Ni–Pd hydrogels were synthesized through sol–gel polycondensation followed by ambient drying. The aim of this study was the determination of the effect of heat treatment in air at 450 °C on the properties of C–Ni–Pd gels prepared using different Pd salts. In the present work, Ni was added as acetate whereas Pd was added as acetate (CA–Ni–Pd) and as chloride (CB–Ni–Pd). Samples were examined by scanning electron microscopy and X-ray diffraction. Surface area was characterized by N₂ adsorption at ?195.5 °C. Thermogravimetric analysis was carried out in order to determine the thermal characteristics of carbon gel and nickel–palladium composites in air atmosphere. CA–Ni–Pd composite had a higher activity and two-phase reaction compared to the CB–Ni–Pd composite. Further improvement of the electrolyte diffusion into the particles of nickel and palladium was obtained by oxidative thermal treatment. During this process a structural modification of the material took place, consequently leading to changes in the electrochemical properties of the composites.     

The influence of the mixed alkaline earth effect on the structure and properties of (Ca,Mg)–Si–Al–O–N glasses

Alkaline earth oxynitride glasses of (Ca, Mg)–Si–Al–O–N with different CaO/(CaO + MgO) molar ratios (0, 0.25, 0.5, 0.75, and 1) were successfully prepared using the sol-gel method, and their structural compositions were characterised by Raman and FT-IR techniques. The glass dynamic properties of thermal expansion coefficient, glass transition temperature (T_g), and static properties of density, molar volume, Vickers hardness and compressive strength were systematically measured and analysed. The results showed that the static properties exhibited an overall regular change as the CaO/(CaO + MgO) ratio gradually increased, while the dynamic properties had an obvious mixed alkaline earth effect, which represented the appearance of an extreme value point in CaO/(CaO + MgO) mole ratios of 0.25 and 0.75, respectively. The typical thermal expansion coefficient and T_g of mixed alkaline earth oxynitride glasses deviated far from the linear connection between single alkaline earth oxynitride glasses. Raman spectra and infrared spectra revealed that the ratio value of the Q³/(Q²+Q⁴) decreased (Qⁿ: n = no. of bridging anions joining SiO₄ tetrahedra) in the mixed alkaline earth oxynitride glasses with increasing the amount of Ca, confirming that Ca decreased the crosslinking between individual tetrahedra via the transformation of Q³ species into Q² and Q⁴ species.     

The effect of the surface nanostructure and composition on the antiwear properties of zirconia–titania coatings

This study describes the preparation, surface imaging and tribological properties of titania coatings modified by zirconia nanoparticles agglomerated in the form of island-like structures on the titania surface. Titania coatings and titania coatings with embedded zirconia nanoparticles were prepared by the sol–gel spin coating process on silicon wafers. After deposition the coatings were heat-treated at 500 °C or 1000 °C. The natural tendency of nanoparticles to form agglomerates was used to build separated island-like structures unevenly distributed over the titania surface having the size of 1.0–1.2 μm. Surface characterization of coatings before and after frictional tests was performed by atomic force microscopy (AFM) and optical microscopy. Zirconia nanoparticles were imaged with the use of transmission electron microscopy (TEM). The tribological properties were evaluated with the use of microtribometer operating in ambient air at technical dry friction conditions under normal load of 80 mN. It was found that nanocomposite coatings exhibit lower coefficient of friction (CoF) and considerably lower wear compared to titania coating without nanoparticles. The lowering of CoF is about 40% for coatings heated at 500 °C and 33% for the coatings heated at 1000 °C. For nanocomposites the wear stability was enhanced by a factor of 100 as compared to pure titania coatings. We claim that enhanced tribological properties are closely related to the reduction of the real contact area, lowering of the adhesive forces in frictional contacts and increasing of the composite hardness. The changes in materials composition in frictional contact has secondary effect.     

The effect of CuO–ZnO–Al2O3 catalyst structure on the ethanol synthesis from syngas

CuO–ZnO–Al₂O₃ catalysts were prepared by complete liquid phase technology with different addition sequences. The results indicated that the catalyst prepared by the addition of (C₃H₇O)₃Al to Cu(NO₃)₂ and Zn(NO₃)₂ solutions shows excellent ethanol selectivity at the initial stages of reaction, reaching approximately 40%. X-ray photoelectron spectroscopy results showed that ethanol synthesis requires a higher Cu⁺ content and higher Cu/Zn ratio on the catalyst surface. The temperature-programmed reduction test revealed strong interactions between Cu species and zinc or aluminum oxide. The increase in the difficulty of catalyst reduction indicated higher ethanol selectivity.     

Oligomers distribution at the gel point of tannin–formaldehyde thermosetting adhesives for wood panels

Tannin–formaldehyde (TF) thermosetting wood adhesives for panel products for the building industry were examined to determine which oligomers were formed during the reaction between tannin and formaldehyde. The reaction products were examined by Matrix Assisted Laser Desorption/Ionization Time of Flight mass spectrometry. The analysis revealed that at the gel point, the adhesive was composed of unreacted flavonoid monomers and some oligomers, and due to reaction with formaldehyde, of methylolated tannin monomers and oligomers as well as flavonoids linked by methylene bridges. The slow gelling conditions used to prepare the TF hydrogel caused the unusual occurrence that not only the flavonoid units A-rings but also pyrogallol-type B-rings of the flavonoid units started to react with formaldehyde at the low pHs between 6 and 7 used for tannin adhesives and contributed to the network formed. This reaction was observed for the first time in this study.     

The effect of soluble β-nucleator's content on crystalline structure and performance of polypropylene pipe

Strength-toughness clash of polypropylene (PP) pipe is an insurmountable bottleneck for the potential application. Here, we successfully prepared PP pipe with simultaneously enhanced toughness and hoop strength via addition of soluble β-nucleators (β-NAs) and application of helical flow in the extrusion. The outstanding combination of strength and toughness in the PP pipe depended on the loading content of β-NAs and the helical pattern, which determined the morphology and alignment of β-crystals. At the low content, β-NAs dissolved completely into the PP melts and distributed homogeneously to promote the formation of β-spherulites in the PP pipe. When the loading content exceeded the solubility limit, the β-NAs partially dissolved and upon cooling, the dissolved β-NAs grew preferentially on the undissolved ones along one direction, assembling into the fibrous aggregates. With the guidance of helical flow, the fibrous β-NAs aligned off the axis and functioned as an oriented template to trigger the PP crystallization on the surface into hybrid β-shish-kebab with fibrous β-NAs as shish. Increasing rotation speed of mandrel and die elevated hoop contribution to obtain the β-shish-kebab with a deviated angle of 55°, endowing the prepared pipe with high hoop strength and toughness.