Curing characteristics of urea–formaldehyde resin in the presence of various amounts of wood extracts and catalysts

The characteristics of urea–formaldehyde (UF) resin curing in the presence of wood extracts and a catalyst [ammonium chloride (NH₄Cl)] were investigated by differential scanning calorimetry (DSC). The effects of extracts from 16 wood species on resin curing behaviors were evaluated. A model developed in this study, T_p = 53.296 exp(?9.72C) + 93.104, could be used to predict the resin curing rate in terms of the DSC peak temperature (T_p) as influenced by the NH₄Cl content (C). The results indicated that the curing rate of UF resin increased as the catalyst content increased and reached a maximum when the catalyst content ranged from 0.5 to 1.0% (solid basis over liquid UF resin weight). Further increases in the catalyst content had no effect on the resin curing rate. The curing rates of UF resin in the presence of wood extracts increased with decreased pH values or increased base buffer capacities. It was also discovered that the activation energy could not fully explain the resin curing behavior when some species of wood extracts were present, and therefore, the pre‐exponential factor had to be taken into account. The concept of the equivalent catalyst content (ECC) of wood extracts to the NH₄Cl content was introduced in this study; ECCs ranged from 0.0022 to 0.0331% among the 16 wood species. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Relationship between curing activation energy and free formaldehyde content in urea-formaldehyde resins

This study investigated the effect on the curing behavior, activation energy (E _a) of the curing reaction, crystalline structure, crosslinking, and free formaldehyde content of the addition of the following scavengers in urea-formaldehyde (UF) resins: medium density fiber board flour, rice husk flour, silica powder, and tannin powder. The scavenger content was 3 and 7?wt% of the UF resin solid content. The curing behavior of UF resins was monitored by differential scanning calorimetry, thermogravimetric analysis, and X-ray crystallography. The curing E _a was correlated to the free formaldehyde content of the scavenger containing UF resins. The thermal stability of the UF resins increased but the curing E _a decreased with increasing scavenger content. After curing, the crystallinity of the UF resins decreased in the presence of scavengers. The unreacted free formaldehyde content was reduced in the tannin powder containing UF resins. The degree of crosslinking affects the formaldehyde emission from wood panels bonded with UF resin. This is especially true for wood panels in service for long periods of time and exposed to high humidity conditions. Once the free formaldehyde which influences considerably the emission has disappeared, the presence of the –CH₂– groups then becomes important. Hence, an increased resin crosslinking indicates a higher concentration of –CH₂– groups present, which may hydrolyze and emit formaldehyde slowly over time.     

Curing of low level melamine‐modified urea‐formaldehyde particleboard binder resins studied with dynamic mechanical analysis (DMA)

Effects of resin formulation, catalyst, and curing temperature were studied for particleboard binder‐type urea‐formaldehyde (UF) and 6 ～ 12% melamine‐modified urea‐melamine‐formaldehyde (UMF) resins using the dynamic mechanical analysis method at 125 ～ 160°C. In general, the UF and UMF resins gelled and, after a relatively long low modulus period, rapidly vitrified. The gel times shortened as the catalyst level and resin mix time increased. The cure slope of the vitrification stage decreased as the catalyst mix time increased, perhaps because of the deleterious effects of polymer advancements incurred before curing. For UMF resins, the higher extent of polymerization effected for UF base resin in resin synthesis increased the cure slope of vitrification. The cure times taken to reach the vitrification were longer for UMF resins than UF resins and increased with increased melamine levels. The thermal stability and rigidity of cured UMF resins were higher than those of UF resins and also higher for resins with higher melamine levels, to indicate the possibility of bonding particleboard with improved bond strength and lower formaldehyde emission. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 377–389, 2005     

Effect of wood on the curing behavior of commercial phenolic resin systems

Differential scanning calorimetry (DSC) was used to study the effect of wood on the curing behavior of two types of commercial oriented‐strand‐board phenolic resins. DSC analysis showed that the curing behavior of the core resin differed significantly from that of the face resin in terms of the peak shape, peak temperature, and activation energy. The addition of wood to the resins moved the two separated peaks in the DSC curves of the core resin adjacent to each other. It also accelerated the addition reactions in the curing processes of both the core and face resins. The two peaks in the DSC curves were the result of the high pH values of the resins. These two peaks became either jointed together or overlapped when the pH value of the resin was reduced. Wood also reduced the activation energies for both the core and face resins by decreasing the pH values of the curing systems. Moreover, the effects of wood on the curing behavior of the resins among the five species studied were similar. The lowest activation energy for a phenolic resin probably appeared at pH 10–11 under alkaline conditions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 185–192, 2005     

Influence of glyoxal on curing of urea-formaldehyde resins

In the present paper, the effect of glyoxal on the gel formation within the adhesive systems based on urea-formaldehyde (UF) resins is shown. A reduction of formaldehyde content in wood-based panels by decreasing the formaldehyde/urea molar ratio in the UF resins leads to increasing of the UF resin gel time, and impairing the qualitative characteristics of the UF-based wood materials. Glyoxal is shown to speed up the crosslinking of the macromolecules as well as significant reduction of gel time of adhesive composition. The first reason is the result of reaction between glyoxal and ammonium ion leading to protons releasing. Another reason is that glyoxal and its interaction products react with macromolecules of the UF resin forming a three-dimension cross-linked structure. The gel time and the pot life of the UF resin are measured by the oscillatory viscometer. Formation of the UF cross-linked resin structure with glyoxal and a curing catalyst (ammonium sulfate) is studied using dispersion Raman scattering spectroscopy. Particleboards (PB) are produced using different amount of glyoxal and formaldehyde/urea molar ratio in the UF resin. The properties are evaluated according to the European Standards and include density, internal bond, thickness swelling moisture content and formaldehyde content.     

Assessment of thermal behavior of pre-curing UF resin with different heat treatment

The thermal behavior of pre-curing urea–formaldehyde (UF) resin with different solid content was investigated by different scanning calorimetry (DSC), and the activation energies (E_a) in different pre-curing stage of UF resin were also analyzed by Kissinger method. The results indicated that with pre-curing degree increasing, the DSC curves of pre-curing UF resin shifted to lower temperature, and both the onset and peak temperature decreased. The pre-curing process of UF resin included two stages: In the first stage, the E_a and Z value decreased obviously due to the activity of component increased with water evaporation, and then, these two values increased in the second stage due to pre-curing degree increased even partial resin was cured.     

Urea–formaldehyde‐resin gel time as affected by the pH value,solid content,and catalyst

An experiment was conducted to investigate the effects of the resin solid content, catalyst content, and pH value obtained by the addition of two kinds of catalysts on the gel time of a urea–formaldehyde (UF) resin. Upon the addition of ammonium chloride, the pH value of the resin mixture decreased to 7 but not significantly further because of the limited free formaldehyde in the system. The pH values of the critical points, at which the resin‐curing rate dramatically increased and the gel time was reduced, were above 7 for both catalysts. To achieve the same gel time, the required pH value of the UF resin adjusted with ammonium chloride was higher than that of the resin modified by hydrochloric acid. This indicated that the main effects of ammonium chloride on the UF‐resin cure included both the release of hydrochloric acid and the catalysis of the reactants in the UF‐resin system. The gel time of the UF resin obviously decreased with increasing catalyst and resin solid contents and with decreasing pH. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1566–1569, 2007     

Effect of microfibrillated cellulose addition on thermal properties of three grades of urea-formaldehyde resin

Three grades of liquid urea-formaldehyde (UF) resin with different formaldehyde emission levels such as super E0 (SE0), E0 and E1 were modified by adding different amounts of microfibrillated cellulose (5 wt% MFC and 95 wt% water) that had been isolated by mechanical disintegration of pulp fibers. Thermal properties of these UF resins were investigated to understand thermal curing and degradation behaviors of the modified UF resins, using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The DSC thermograms showed an exothermic curing reaction, and the curing peak temperature of modified UF resins heavily depended on the emission resin grade with an increasing order from E1, E0 to SE0. The addition of MFC suspension into the UF resins gradually increased curing peak temperature suggesting a decrease in the resin reactivity. TGA results showed three main thermal degradation temperatures for the modified UF resins except the SE0 UF resin, which had four degradation temperatures.     

Cure behavior of epoxy resin containing castor oil and cashew nut shell liquid and its derivative

The cure behavior of epoxy resin with a conventional amide‐type hardener (HD) was investigated in the presence of castor oil (CO), cashew nut shell liquid (CNSL), and cashew nut shell liquid–formaldehyde resin (CFR) with dynamic differential scanning calorimetry (DSC). The activation energy of the curing reaction was also calculated on the basis of nonisothermal DSC thermograms at various heating rates. A one‐stage curing was noted in the case of epoxy resin filled with CO, whereas the epoxy resin with CNSL and CFR showed a two‐stage curing process. A competitive cure reaction was noted for the epoxy resin/CNSL(or CFR)/HD blends. In the absence of HD, CFR showed lower values of curing enthalpy than that of CNSL. The activation energy of epoxy resin curing increased with increasing CNSL and CFR loading. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Properties of liquefied wood modified melamine-formaldehyde (MF) resin adhesive and its application for bonding particleboards

In this study, we modified melamine-formaldehyde (MF) resin adhesive with liquefied wood (LW) and determined the properties of MF–LW adhesive mixtures. Furthermore, we produced particleboards using prepared MF–LW mixtures and evaluated their mechanical and physical properties. Results showed that with increasing content of LW in the adhesive mixture gel time and peak temperature increased while reaction enthalpy decreased. With increasing substitution of MF resin adhesive with LW the thermal stability of adhesive mixture reduced, namely thermal degradation started at lower temperature and weight loss increased. Properties of particleboards improved with increasing amount of LW in the adhesive mixture up to 20% and then deteriorated. Nevertheless, the properties of particleboard with 30% LW in the adhesive mixture were comparable to the properties of particleboard without LW while they worsen at greater portion of LW. Consequently, MF resin adhesive with 30% LW substitution could be used to produce particleboards with suitable mechanical properties and reduced formaldehyde release content.     

Differential scanning calorimetry of urea–formaldehyde adhesive resins,synthesized under different pH conditions

The purpose of this study was to investigate the effects of reaction pH conditions on thermal behavior of urea–formaldehyde (UF) resins, for the possible reduction of formaldehyde emission of particleboard bonded with them. Thermal curing properties of UF resins, synthesized at three different reaction pH conditions, such as alkaline (pH 7.5), weak acid (pH 4.5), and strong acid (pH 1.0), were characterized with multiheating rate method of differential scanning calorimetry. As heating rate increased, the onset and peak temperatures increased for all three UF resins. By contrast, the heat of reaction (ΔH) was not much changed with increasing heating rates. The activation energy (E_a) increased as the reaction pH decreased from alkaline to strong acid condition. The formaldehyde emission of particleboard was the lowest for the UF resins prepared under strong acid, whereas it showed the poorest bond strength. These results indicated that thermal curing behavior was related to chemical species, affecting the formaldehyde emission, while the poor bond strength was believed to be related to the molecular mobility of the resin used. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 422–427, 2006     

Effects of formaldehyde to urea mole ratio on thermal curing behavior of urea–formaldehyde resin and properties of particleboard

As a part of abating the formaldehyde emission (FE) of urea–formaldehyde (UF) resin, this study was conducted to investigate the effects of formaldehyde to urea (F/U) mole ratio on thermal curing behavior of UF resins and properties of PB bonded with them. UF resins synthesized at different F/U mole ratios (i.e., 1.6, 1.4, 1.2, and 1.0) were used for the manufacture of PB. Thermal curing behavior of these UF resins was characterized using differential scanning calorimetry (DSC). As the F/U mole ratio decreases, the gel time, onset and peak temperatures, and heat of reaction (ΔH) increased, while the activation energy (E_a) and rate constant (k) were decreased. The amount of free formaldehyde of UF resin and FE of PB prepared decreased in parallel with decreasing the F/U mole ratio. The internal bond strength, thickness swelling, and water absorption of PB was slightly deteriorated with decreasing the F/U mole ratio of UF resins used. These results indicated that as the F/U mole ratio decreased, the FE of PB was greatly reduced at the expense of the reactivity of UF resin and slight deterioration of performance of PB prepared. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1787–1792, 2006     

The reaction in water of UF resins with isocyanates at short curing times: A 13C NMR investigation

CP MAS ¹³C NMR spectra of hardened resins have shown that urethane bridges derived from the reaction of the isocyanate group with the hydroxymethyl group of urea do form even at fast curing times comparable to what was used in the wood panels industry, in lower proportions than what was shown earlier. Polyureas and biurets obtained from the reaction of isocyanate with water are the predominant crosslinking reactions of pMDI alone and in UF/pMDI resin systems under fast curing conditions. Residual, unreacted isocyanate groups in the hardened network are consistently observed. Their proportion markedly decreases when the original proportion of urea–formaldehyde (UF) resin is high and that of pMDI is low. Under these fast curing conditions, the UF resin appears to self‐condense through an unusually high proportion of methylene ether links rather than methylene bridges alone. A marked proportion of residual, unreacted hydroxymethyl groups is also noticeable, initially, in the UF self‐condensation network. Direct NMR tests on thin hardboard bonded under fast pressing conditions with different proportions of UF/pMDI confirmed that crosslinking due to polyureas and biurets formation are predominant in the crosslinking of pMDI when alone and in UF/pMDI resin systems. They confirmed that residual, unreacted isocyanate groups are present in the finished panel. Their proportion is higher when the proportion of pMDI in the system is high. The presence or absence of urethanes could not be confirmed directly on the panels as the relevant peaks are masked by the wood carbohydrates signals of wood cellulose and hemicelluloses. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1624–1632, 2006     

Effect of synthesis parameters on thermal behavior of phenol–formaldehyde resol resin

Differential scanning calorimetry (DSC) was used to investigate the influence of resin synthesis parameters on the thermal behavior of low molecular weight phenol–formaldehyde (PF) resol resins prepared with different formaldehyde/phenol (F/P) molar ratios, different sodium hydroxide/phenol (NaOH/P) molar ratios, and different catalysts. As the F/P molar ratio increased, the molecular weight and activation energy increased while the gel time, peak temperature, resin pH, and nonvolatile solids content decreased. By contrast, the molecular weight, gel time, resin pH, resin solids content, and peak temperature increased with an increasing NaOH/P molar ratio. However, the activation energy decreased with an increasing NaOH/P molar ratio. The polydispersity increased with both F/P and NaOH/P ratios. Calcium hydroxide gave a faster curing resin compared to sodium and potassium hydroxides. All DSC thermograms of this study showed just a single exothermic peak for the resins that were used. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1415–1424, 2002     

Effect of the resin/hardener ratio on curing,structure and glass transition temperature of nanofilled epoxies

The curing reaction, structure, and glass transition behavior of epoxy‐clay nanocomposites prepared using several different resin/hardener ratios were investigated. Nonisothermal DSC experiments evidenced that the incorporation of the organoclay did not induce appreciable changes in the curing enthalpy, but determined a slight acceleration of the curing reaction, without modifying the activation energy. TEM and SEM analyses of the nanocomposite resins showed the presence of micrometric aggregates for all the resin/hardener ratios investigated, even though these materials showed good optical clarity and their WAXD analyses did not evidence any organoclay peak. In addition, the higher the hardener content, the lower the tendency toward exfoliation and the broader the distribution of the interlamellar distances. The degree of cross‐linking of cured resins was evaluated both from measurements of the elastic modulus in the rubbery plateau and from solvent sorption experiments. A maximum in cross‐link density was observed near the stoichiometric composition. Both modulus and sorption experiments suggested that filler‐matrix adhesion increased with increasing the resin/hardener ratio, a trend that was confirmed also by glass transition temperature data. An analysis of ethyl acetate sorption curves evidenced that a gradual transition from Fickian to Case II diffusion occurred as the resin/hardener ratio was raised and that the organoclay promoted deviation from the Fickian behavior. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

聚苯醚/环氧体系非等温固化行为及固化工艺

采用程序升温差示扫描量热仪（DSC）法,用Kissinger方程研究了聚苯醚（PPE）/环氧（EP）体系不同配比混合物的固化反应动力学特征。非等温DSC研究表明PPE/EP体系的固化反应过程比较复杂,其动力学参数受PPE含量的影响较大,PPE/EP混合物的固化反应起始温度随PPE含量的增大而增大,最大放热峰的峰温均随着PPE含量的增加而减小。Kissinger法计算得到PPE/EP体系10% PPE、20% PPE、40% PPE含量（质量）的表观活化能依次为63.88、55.37、47.31 kJ·mol^-1, 说明PPE可以促进环氧树脂的固化反应。在此基础上,以20% PPE/EP体系为例,采用T - β 图外推法,得到了其固化工艺     

The kinetics of B‐a and P‐a type copolybenzoxazine via the ring opening process

The structure of benzoxazines is similar to that of phenolic resin through thermal self‐curing of the heterocyclic ring opening reaction that neither requires catalyst nor releases any condensation byproduct. These polybenzoxazine resins have several outstanding properties such as high thermal stability and high glass transition temperature. To better understand the curing kinetics of this copolybenzoxazine thermosetting resin, dynamic and isothermal differential scanning calorimetry measurements were performed. Three models, the Kissinger method, the Flynn–Wall–Osawa method, and the Kamal method, were used to describe the curing process. Dynamic kinetic activation energies based on Kissinger and Flynn–Wall–Osawa methods are 72.11 and 84.06 KJ/mol, respectively. The Kamal method based on an autocatalytic model results in a total order of reaction between 2.66 and 3.03, depending on curing temperature. Its activation energy and Arrhenius preexponential are 50.3 KJ/mol and 7959, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 730–737, 2005     

Some filler effects on cross-linking of unsaturated polyesters

The effect of five fillers on the cross-linking macro-and microcharacteristics of simple unsaturated polyester resins was investigated by differential scanning calorimetry (DSC), reactivity tests, and gel time tests. Glass beads and silica flour appeared to have little influence on the cross-linking reaction of the resin itself, their effect being comparable to mere dilution of the resin. Kaolin presented some interaction with the resin due to its absorption characteristics and acid groups. Reground polyester/glass fiber powder and especially wood flour appeared to present clear chemical interactions with the curing behavior of the resin. Wood flour, in particular, was shown by DSC analysis to strongly co-react with the resin during cross-linking and altered markedly the resin enthalpy change and energy of activation during curing. The wood flour component causing the altered behavior of the resin appears to be lignin. DSC analysis of resins filled with three different types of isolated lignins indicated that this wood flour component reacts in a heterogeneous phase reaction with the resin during cross-linking. It appears that it is the lignin unsaturated carbon–carbon double bonds at the polyester/wood flour and at the polyester/lignin interphases that are likely to co-react by heterogeneous phase radical cross-linking with the polyester resin and styrene unsaturation, markedly changing the resin curing behavior. © 1993 John Wiley & Sons, Inc.     

A cure study on alumina trihydrate reinforced allylester resins by differential scanning calorimetry

Allylester prepolymers were synthesized by transesterification, and curing kinetics of alumina tihydrate reinforced allylester resins was studied by means of a differential scanning calorimetry dynamic experiment. The activation energies and the frequency factors of the reinforced allylester prepolymers were estimated by means of Ozawa's and Kissinger's methods. The values determined from the Ozawa method are higher than those from the Kissinger method. The peak exotherm temperature of reinforced allylester resin was shifted to a lower temperature as the concentration of curing agent increased. The peak exotherm temperature as the concentration of curing agent increased. The peak exotherm temperature of reinforced allylester resin was, however, shifted to a higher temperature as the content of alumina trihydrate increased. In the case of the dynamic experiment, both the activation energy and the frequency factor decreased as the concentration of curing agent was increased. Meanwhile, there exist minimum values of both the activation energy and th frequency factor with varying contents of alumina trihydrate.     

Monitoring the curing of furan resins through the exothermic heat of reaction

The curing reaction of furan resins was monitored through the exothermic heat of reaction by means of a simple technique. p-Toluene sulphonic acid dissolved in acetone was used to catalyse the curing reaction. A ‘cure rate index’, defined as the maximum temperature rise per unit time per unit mass of the resin, was used as a measure of the rate of cure. The index value increases exponentially with the catalyst concentration. Interestingly, for the same catalyst concentration the index value also increases significantly with the period of ageing of the catalyst solution. A method is developed for deriving the activation energy for the curing reaction from the exothermic heat data for non-isothermal cure. The activation energy is found to increase with resin viscosity and to decrease exponentially with increasing catalyst concentration. Quantitative expressions are derived relating activation energy with catalyst concentration.