Guanben Du

Microwave Drying of Wood Strands

Abstract Characteristics of microwave drying of wood strands with different initial moisture contents and geometries were investigated using a commercial small microwave oven under different power inputs. Temperature and moisture changes along with the drying efficiency were examined at different drying scenarios. Extractives were analyzed using gas chromatography/mass spectrometry (GC/MS). The results showed that the microwave drying process consisted of three distinct periods (warm-up period, evaporation period, and heating-up period) during which the temperature, moisture change, and drying efficiency could vary. Most of the extractives were remnant during microwave drying. It was observed that with proper selections of power input, weight of drying material, and drying time, microwave drying could increase the drying rate, save up to 50% of energy consumption, and decrease volatile organic compound (VOC) emissions when compared with the conventional drying method.

Study on the Soy Protein-Based Wood Adhesive Modified by Hydroxymethyl Phenol

To explain the reason why using phenol-formaldehyde (PF) resin improves the water resistance of soy-based adhesive, the performance of soy-based adhesive cross-linked with hydroxymethyl phenol (HPF) and the reaction between HPF and a common dipeptide N-(2)-l-alanyl-l-glutamine (AG) being used as a model compound were studied in this paper. The DSC and DMA results indicated the reaction between HPF and soy-based adhesive. The soy-based adhesive cross-linked with HPF cured at a lower temperature than the adhesive without HPF. The former showed better mechanical performance and heat resistance than the latter. The ESI-MS, FT-IR and 13C-NMR results proved the reaction between HPF and AG. Because of the existence of branched ether groups in the 13C-NMR results of HPF/AG, the reaction between HPF and AG might mainly happened between hydroxymethyl groups and amino groups under a basic condition.

Urea–formaldehyde resin prepared with concentrated formaldehyde

Abstract The characteristics of UF resin prepared with concentrated formaldehyde were studied in this paper. With the molar ratio F/U = 1.1, the UF resin prepared with concentrated formaldehyde showed better mechanical properties than that with formalin. The 13C-NMR and FTIR results indicated that there were more methylene groups, ether groups and urons in a UF resin system prepared with concentrated formaldehyde than those in a normal UF resin. The differential scanning calorimetry and DMA results showed that the curing temperature of UF resin with concentrated formaldehyde was lower than that of a normal UF resin. UF resin with concentrated formaldehyde showed worse thermal stability and higher thermal decomposition temperature.

Soy-Based Adhesive Cross-Linked by Phenol-Formaldehyde-Glutaraldehyde

To prepare a low-formaldehyde soy-based adhesive with good water resistance, phenol-formaldehyde modified with glutaraldehyde (PFG) with lower free phenol and free formaldehyde contents was used to cross-link the soy-based adhesive. The results showed that the mechanical properties and water resistance of plywood prepared with soy-based adhesive with PFG was better than that of plywood with the same amount of phenol-formaldehyde (PF). The reaction between phenol and glutaraldehyde was proved by 13C-NMR. Under the optimized preparation conditions for plywood, that is to say, press temperature 160 °C, press time 4 min and resin loading 320 g·m−2, type I plywood could be prepared with 9% PFG as a cross-linker of soy-based adhesive. The Differential Scanning Calorimetry (DSC) result confirmed the cross-linking reaction between soy-based adhesive and PFG or PF. The activation energy of soy-based adhesive with cross-linker PFG was higher than that with PF resin.

The Influence of pH on the Melamine-Dimethylurea-Formaldehyde Co-Condensations: A Quantitative 13C-NMR Study

1,3-dimethylurea (DMU) was used to mimic urea and to model melamine-urea-formaldehyde (MUF) co-condensation reactions. The products of 1,3-dimethylurea-formaldehyde (DMUF), melamine-formaldehyde (MF), and melamine-1,3-dimethylurea-formaldehyde (MDMUF) reactions under alkaline and weak acidic conditions were compared by performing quantitative carbon-13 nuclear magnetic resonance (13C-NMR) analysis. The effect of pH on the co-condensation reactions was clarified. With the presence of the methyl groups in DMU, the appearance or absence of the featured signal at 54–55 ppm can be used to identify the co-condensed methylene linkage –N(–CH3) –CH2–NH–. Under alkaline condition, MDMUF reactions produced primarily MF polymers and the featured signal at 54–55 ppm was absent. Even though the co-condensations concurrently occurred, undistinguishable and very minor condensed structures with ether linkage were formed. Differently, under weak acidic condition, the relative content of co-condensed methylene carbons accounts for over 40%, indicating the MDMUF co-condensation reactions were much more competitive than the self-condensations. The formation of reactive carbocation intermediate was proposed to rationalize the results.

Urea-formaldehyde resin structure formation under alkaline condition: a quantitative 13C-NMR study

Abstract The urea-formaldehyde (UF) reaction under strong alkaline condition was investigated by using quantitative analysis of 13C NMR. The main reaction products were methylolureas and oligomers linked by ether bonds at the beginning stage. With the reaction undergoing, the methylene linkages began to be formed and become predominant at the end point. The conversion of linear methylene ether bond to methylene linkage was also observed. These features were also observed previously for the reaction under acidic condition. It was found that the cyclic ether structure (uron) is much more stable than the linear ether bond, and its stability is second only to the methylene linkages among all the condensed structures. The formaldehyde was consumed in fast Cannizarro reaction under strong alkaline condition, producing considerable amount of methanol, which is the main negative aspect of this condition. With the exception of the differences caused by Cannizarro reaction, the UF production reactions under alkaline and acidic conditions are similar. The pH did not change the thermodynamic nature of the involved reactions, but only changed the competitive relationships of different reactions in kinetics.

Theoretical Confirmation of the Quinone Methide Hypothesis for the Condensation Reactions in Phenol-Formaldehyde Resin Synthesis

The mechanisms for the base-catalyzed condensation reactions in phenol-formaldehyde resin synthesis were investigated by using the density functional theory method. The structures of the intermediates and transition states, as well as the potential energy barriers of the involved reactions, were obtained. The hypothesis of quinine methide (QM) formation was theoretically confirmed. Two mechanisms were identified for QM formation, namely E1cb (elimination unimolecular conjugate base) and water-aided intra-molecular water elimination. The latter is energetically more favorable and is proposed for the first time in this work. Based on the QM mechanism, the condensation should be a unimolecular reaction because the following condensation between an ionized species (dissociated phenol or hydroxymethylphenol) with QM is much faster. The previously proposed SN2 condensation mechanism was found to be not competitive over the QM mechanism due to a much higher energy barrier. The condensation reaction between neutral phenol or hydroxymethylphenol and QM was also found to be possible. The energy barrier of this reaction is close to or higher than that of QM formation. Therefore, the overall condensation reaction may appear to be bimolecular if such a reaction is incorporated. The theoretical calculations in this work rationalized the discrepant results reported in previous kinetics studies well.

A Novel Fiber–Veneer-Laminated Composite Based on tannin resin

ABSTRACT Natural nonwoven fiber was impregnated with a tannin resin and laminated with wood veneer for preparation of laminated composites. The tannin resin used showed a good compatibility with the natural fiber, and was easy to assemble with the wood veneers. The tannin resin penetration into the wood veneer was observed by light microscopy. The laminated composite shows very good mechanical properties and water resistance. Shear force–displacement testing demonstrates that the laminated composite had a ductile behavior under wet testing conditions. The laminated composite was prepared using 100% natural biorenewable raw materials and had good properties compared to conventional plywood bonded with synthetic resin.

A 13C-NMR Study on the 1,3-Dimethylolurea-Phenol Co-Condensation Reaction: A Model for Amino-Phenolic Co-Condensed Resin Synthesis

The reactions of di-hydroxymethylurea with phenol under alkaline (pH = 10), weak (pH = 6) and strong acidic (pH = 2) conditions were investigated via the 13C-NMR method. Based on the proposed reaction mechanisms, the variations of the structures of different condensed products were analyzed and the competitive relationship between self- and co-condensation reactions was elucidated. The required experimental conditions for co-condensations were clearly pointed out. The main conclusions include: (1) the self-condensation between urea formaldehyde (UF) or phenol formaldehyde (PF) monomers were dominant while the co-condensations were very limited under alkaline conditions. This is because the intermediates produced from urea, methylolurea and phenol are less reactive in co-condensations with respect to self-condensations; (2) under weak acidic conditions, the self-condensations occurred exclusively among the UF monomers. The co-condensation structures were not observed; and (3) the co-condensations became much more competitive under strong acidic conditions as the relative content of the co-condensed methylenic carbon accounts for 53.3%. This result can be rationalized by the high reactivity of the methylolphenol carbocation intermediate toward urea and methylolurea. The revealed reaction selectivity and mechanisms may also be applied to the synthesis of those more complex co-condensed adhesives based on natural phenolic and amino compounds.

Soy-based adhesive cross-linked by melamine–glyoxal and epoxy resin

Abstract To develop a soy-based adhesive with good water resistance, non-toxic melamine–glyoxal resin (MG) prepared in the laboratory was used as a cross-linker of soy-based adhesive. The FT-IR and ESI-MS results showed that there was a reaction between melamine and glyoxal. The resulted –CH–OH– groups could be the possible reactive groups for the cross-linking of soy-based adhesive. The wet shear strength of soy-based plywood indicated that the water resistance of soy adhesive cross-linked by MG improved with respect to that with no cross-linker, although it was not good enough to satisfy the relative standard. With the optimized preparation procedures for plywood, specifically, press temperature 180 °C, press time 3 min and resin loading 280 g m−2, type I soy-based plywood could be prepared with a hybrid cross-linker, namely 12%MG + 2% epoxy resin (EPR). The DSC results showed that the reaction between soy-based adhesive and the hybrid cross-linker MG + EPR was very complex.