Polyamine-modified urea–formaldehyde-bonded wood joints. III. Fracture toughness and cyclic stress and hydrolysis resistance

The objective of this study was to improve the durability and stability of urea–formaldehyde-bonded wood products by decreasing the internal stress developed during the resin cure and by improving the ability of the cured system to withstand cyclic stresses. Urea–formaldehyde resins were modified either by incorporating urea-capped di-and trifunctional amines into the resin structure or by using the hydrochloride derivatives of some of these amines as the curing agent, or by both methods. This study supplements our previous work by examining the effects of additional amines and subjecting bonded products to additional testing. Solid wood joints bonded with a variety (7 of 15) of modified adhesives had resistance to cyclic stress superior compared to that of joints bonded with unmodified urea–formaldehyde adhesive; at least three of the modified adhesives approached the behavior of phenol–formaldehyde-bonded joints. Resistance to moist heat aging, although still inferior to that of phenol–formaldehyde-bonded joints, was significantly improved for joints bonded with modified adhesives over joints made with unmodified resins. The fracture behavior of joints made with modified adhesives was different from that of joints made with unmodified resins. The fracture energy was greater for joints made with three of four modified adhesives than for joints made with unmodified resins. Modified adhesives produced particleboards made with enhanced cyclic stress resistance. Formaldehyde emission from particleboards made with resins modified with urea-terminated amines was less than emission from boards made with unmodified resins. However, emissions from particleboards made with amine hydrochlorides were not improved compared to those from boards made with an ammonium chloride curing agent. © 1993 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

Polyamine-modified urea-formaldehyde resins. I. Synthesis,structure, and properties

The objective of this study was to improve the durability and stability of urea–formaldehyde-bonded wood products by decreasing the internal stress developed during resin cure and by improving the ability of the cured resin to withstand cyclic stresses. This paper presents initial results from modifying a urea–formaldehyde resin by incorporating di- and trifunctional amines. The amines were incorporated by adding them as amines during resin synthesis, by adding urea-capped amines during resin synthesis, and by using amine hydrochlorides as acidic curing agents. Addition of amines during resin synthesis produced uncurable resins. However, modification with urea-capped amines or curing with amine hydrochlorides provided cure rates comparable to that of unmodified resin cured with ammonium chloride. These modifications also reduced the tendency of the resin to crack and fracture and substantially improved the resistance of bonded joints to cyclic stress imposed by cyclic wet–dry exposures. Resins cured with amine hydrochlorides had lower formaldehyde liberation than those cured with ammonium chloride. Thus, incorporation of flexible di- and triamines offers promise for improving the durability and stability of urea–formaldehyde-bonded wood products.     

Behavior of amine-modified urea–formaldehyde-bonded wood joints at low formaldehyde/urea molar ratios

Urea–formaldehyde-bonded wood products are limited to interior nonstructural applications because of their poor durability under cyclic moisture or humid environments. The stability of solid-wood joints and particleboards can be enhanced by bonding with urea–formaldehyde adhesives modified with di- and trifunctional amines at an effective resin formaldehyde-to-urea mol ratio (F/U) of 1.6; however, particleboard formaldehyde emissions were not improved over those from boards made with unmodified adhesives and were unacceptably high. The relative effectiveness of selected modifications was investigated at resin form aldehyde-to-urea (F/U) molar ratios of 1.4 and 1.2 Solid-wood joints and particleboards made with modified adhesives, an unmodified adhesive, and a phenol formaldehyde (PF) resin were subjected to cyclic soak-dry (cyclic stress) treatments and moist-heat aging. Formaldehyde emissions from particleboards were also determined. At F/U 1.4, the resistance of solid-wood joints made with modified adhesives to cyclic stress and moist-heat aging was equal to that of PF-bonded joints and superior to that of joints bonded with unmodified adhesive. The resistance of particleboards made with modified adhesives was greater than that of boards made with unmodified adhesive but less than that of PF-bonded board. Solid-wood joints and particleboards made with F/U 1.4 resins performed better than did those made with F/U 1.2 resins. Particleboards made with F/U 1.2 resins had formaldehyde emissions well below the standard, and room temperature aging or bonding at high temperature reduced emissions substantially. © 1994 John Wiley & Sons, Inc. 1

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

Use of organosolv lignin in phenol-formaldehyde resins for particleboard production: II. Particleboard production and properties

The objective of this work was to demonstrate the utility of lignin-based resins designed for application as an adhesive in the production of particleboard. Bond qualities of lignin-phenol-formaldehyde resins, phenolated-lignin-formaldehyde resins and commercial phenol-formaldehyde (PF-com) resin were assessed by using an automatic bonding evaluation system, prior to production of particleboards. In order to evaluate the quality of lignin-based resins, particleboards were produced and physical and mechanical properties were investigated. These physical properties included internal bond, modules of rupture and modulus of elasticity. Thickness swell and water absorption properties of particleboards bonded with lignin-based resins were also determined. The lignin-based resins have been reported previously in Part I of this study. The results showed that particleboards bonded with phenolated-lignin formaldehyde resins (up to 30% lignin content) exhibited similar physical and mechanical properties when compared to particleboards bonded with PF-com. The work has indicated that phenolated-lignin formaldehyde resins (up to 30% substitution level) can be used successfully as a wood adhesive for constructing particleboard. The performance of these panels is comparable to those of boards made using PF-com resin.     

Differential scanning calorimetry and dynamic mechanical analysis of amine-modified urea–formaldehyde adhesives

Urea–formaldehyde (UF) resins are susceptible to stress rupture and hydrolytic degradation, particularly under cyclic moisture or warm, humid conditions. Modification of UF resins with flexible di- and trifunctional amines reduces this problem. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used to study the thermal behavior of modified and unmodified adhesives to identify the physical and morphological factors responsible for the improved performance. A UF resin modified by incorporating urea–capped poly(propyleneoxidetriamine) during resin synthesis exhibited a higher cure rate and greater cure exotherm than the unmodified resin. Resins cured with a hexamethylenediamine hydrochloride curing agent had slower cure rates than those cured with NH₄Cl. DMA behavior indicated that modified adhesives were more fully cured and had a more homogeneous crosslink density than unmodified adhesives. DMA behavior changed with storage of specimens at 23°C and 50% relative humidity, after previous heating for approximately 20 min at 105°C to 110°C. The initial changes were postulated to occur because of physical aging (increase in density) and continued cure. These were followed by physical breakdown (microcracking) and possibly cure reversion. © 1995 John Wiley & Sons, Inc.     

Urea formaldehyde resin with low formaldehyde content modified by phenol formaldehyde intermediates and properties of its bamboo particleboards

Phenol formaldehyde reaction solution (PFS) was used to synthesize urea–formaldehyde resins (PFSUF resins) with low formaldehyde content. In addition, the prepared PFSUF resins were used as adhesives to bond bamboo particleboards. Mechanical properties, fracture morphology, water absorption ratio, and dimensional stability of bamboo particleboards have been studied by tensile tests, SEM tests, water absorption analysis, and swelling ratio analysis, respectively. The results demonstrate that the main ingredient of PFS is phenol formaldehyde intermediate 2,4,6‐trimethylolphenate and proper amount of PFS can be used to reduce the formaldehyde content of UF resins effectively. The results also show that bamboo particleboards bonded with PFSUF resins exhibit better mechanical properties, water resistance, and dimensional stability than that bonded with pure UF resin. However, the results of TG and mechanical properties analysis exhibit that alternative curing agents to ammonium chloride should be studied to improve the curing properties of the PFSUF resins with low formaldehyde content. Taken together, this work provides a method of preparing environment‐friendly PFSUF resins with low phenol and low formaldehyde content and the prepared resins have potential application in wood industry. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42280.     

Reduction of Formaldehyde Emission from Particleboard by Phenolated Kraft Lignin

The aim of this study was the reduction of formaldehyde emission from particleboard by phenolated Kraft lignin. For this purpose, the lignin was extracted from black liquor and then modified by phenolation. During the urea formaldehyde (UF) resin synthesis different proportions of unmodified and phenolated Kraft lignins (10%, 15%, and 20%) were added at pH = 7 instead of the second urea. Physicochemical properties and structural changes of resins so prepared, as well as the internal bond (IB) strength and formaldehyde emission associated with the panels bonded with them were measured according to standard methods. The Fourier transform infrared (FTIR) analysis of lignin indicated that the content of O–H bonds increased in phenolated lignin while the aliphatic ethers C–O bonds decreased markedly in the modified lignin. Since both synthesis of UF resins and lignin phenolation are carried out under acid conditions, phenolation is an interesting way of modifying lignin for use in wood adhesive. The panels bonded with these resins showed significantly lower formaldehyde emission compared to commercial UF adhesives. The UF resin with 20% phenolated lignin exhibited less formaldehyde release without significant differences in internal bond strength and physicochemical properties compared to an unmodified UF resin. XRD analysis results indicated that addition of phenolated lignin decreased the crystallinity of the hardened UF resins.     

Ionic liquid modified lignin-phenol-glyoxal resin: a green alternative resin for production of particleboards

The aim of this research was to evaluate the properties of particleboard panels bonded with ionic liquid treated lignin- phenol- glyoxal (LPG) resin. For this purpose, soda bagasse lignin was modified by 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) ionic liquid and then various contents of virgin and modified lignin (20, 30 and 40 wt% based on weight of phenol), phenol and glyoxal were used for synthesis of LPG resins. After resin synthesis, thermal and physicochemical properties of the synthesized resins such as curing behavior, gelation time, viscosity, solid content and density were measured. Finally, the resins so prepared were used for laboratory particleboard manufacturing. The panels physical (water absorption, thickness swelling) as well as mechanical (MOE, MOR and internal bond strength) properties were measured according to standard methods. The resins tests indicated that modification of lignin with ionic liquid not only can accelerate the gelation time and increase viscosity, density and solid content of LPG resins but also decrease the temperature required for curing the LPG resins. Based on the results of this work, the mechanical strength and dimensional stability of the particleboards bonded with a LPG resin can be improved by using modified lignin. The particleboards prepared with the LPG resin, using either modified or virgin lignin, presented higher water absorption as well as weaker mechanical strength than those prepared with the control PF resin. However, there does not appear to be any statistically significant difference between the some properties of the panels bonded with the control PF resin and those bonded with the LPG resin containing modified lignin.     

Effect of resin type and content on properties of composite particleboard made of a mixture of wood and rice husk

This study investigated the effect of resin type and content on the dimensional stability and mechanical properties of single-layer composite particleboards made of a mixture of wood particles (70 wt%) and rice husk particles (30 wt%). Two types of resin, urea–formaldehyde (UF) resin and phenol–formaldehyde (PF) resin, were used in the experiments at three different contents which were 8, 10, or 12 wt%. The dimensional stability of the samples was significantly improved by increasing the resin content. When the contents of the UF and PF resins increased from 8 to 12 wt%, the WA values of the samples decreased to18% and 33%, respectively. Similar results were also observed for the TS values. The UF resin bonded samples swelled two times more than the PF resin bonded particleboard. The mechanical properties of the PF resin bonded samples were better than the UF resin bonded samples. When the contents of the UF and PF resins increased from 8% to 12 wt%, the internal bond strength values of the samples increased to 21% and 41%, respectively. The bending strength and modulus of elasticity of the samples were not significantly increased by increasing contents of the UF and PF resins, except for the 12 wt% content.     

Medium‐density particleboards from rice husks and soybean protein concentrate

Rice husks are a valuable agricultural residue produced worldwide with potential applications as a wood substitute in particleboard manufacturing. In this work, the feasibility of producing medium‐density particleboards based on waste rice husks bonded with environmentally friendly adhesives from soybean protein concentrate was analyzed. The mechanical properties, internal bond strength, and water resistance of the obtained panels bonded with the homemade soybean protein concentrate adhesives were compared to those of boards glued with commercial adhesives such as phenol–formaldehyde and urea–formaldehyde resins. An alkaline treatment improved the gluing ability of the soybean protein concentrate. The mechanical properties of the alkali‐treated soybean protein concentrate were comparable to those determined for panels with urea–formaldehyde. The lower water resistance of the alkali‐treated soybean protein concentrate particleboards, compared with that of the formaldehyde‐based resins, was counterbalanced by the advantage of being more environmentally sound, which makes them suitable for applications for which the requirements for water resistance are not stringent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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.     

Upgrading melamine–urea–formaldehyde polycondensation resins with buffering additives. I. The effect of hexamine sulfate and its limits

Iminoamino methylene base intermediates obtained by the decomposition of hexamethylenetetramine (hexamine) stabilized by the presence of strong anions such as SO and HSO, or hexamine sulfate, were shown to markedly improve the water and weather resistance of hardened melamine–urea–formaldehyde (MUF) resins used as wood adhesives and of the wet internal bond strength performance of wood boards bonded with them. The effect was shown to be induced by very small amounts, between 1 and 5 wt % of this material on resin solid content. This strong effect allowed the use of MUF resins of much lower melamine content and also provided good performance of the bonded joints. Because the main effect was also present at the smaller proportion of hexamine as hexamine sulfate, it was not due at all to any increase in the molar ratio of the resin as a consequence of hexamine sulfate addition. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 203–214, 2003     

Improving Hot-Water Resistance of Melamine-Urea-Formaldehyde by Addition of PolyFox PF-151N Polymer

Melamine urea formaldehyde (MUF) thermosetting wood adhesives have poor performance at elevated temperatures and humid conditions. PolyFox PF-151N polymer was mixed at different loadings (0.05, 0.1, 0.5, and 1%) with MUF to improve properties, especially water resistance and bond strength. The physical properties of the optimized MUF/PolyFox PF-151N resins were measured. In order to evaluate the quality of optimized MUF/PolyFox PF-151N resins, particleboards were produced and physical and mechanical properties were investigated.

The results show that it is possible to add PolyFox PF-151N up to 0.1% to the MUF resin without altering the mechanical properties of the commercial MUF. The mechanical properties of the particleboard panels bonded with the optimal MUF/PolyFox PF-151N (99.9/0.1 by weight) resin were considerably increased as compared to the panels glued with neat MUF resin. The use of PolyFox significantly reduced 2-h and 24-h thickness swelling compared to the control panels.     

Alternative to latent catalysts for curing UF resins used in the production of low formaldehyde emission wood-based panels

This paper studies alternative catalysts to ammonium sulfate for curing urea-formaldehyde (UF) resins. When using a latent catalyst like ammonium sulfate, hexamine is formed as by-product of curing reaction. It is believed that hexamine hydrolysis may contribute to formaldehyde release during the life-time of wood-based panels produced with UF resins. Orthophosphoric acid, on the other hand, catalyzes resin cure without by-product formation and was compared to ammonium sulfate. The pot-life of adhesives with both catalysts was evaluated at 40 °C with a Brookfield rheometer. Mechanical resistance tests performed with ABES (Automated Bonding Evaluation System) showed that orthophosphoric acid effectively catalyzes UF resin cure. Particleboards were produced using both catalysts and the most important properties evaluated, according to European Standards: formaldehyde content, internal bond, moisture content, thickness swelling and density. Particleboards cured with orthophosphoric acid and stored under forceful conditions of humidity and temperature presented similar internal bond and lower formaldehyde content than those produced with ammonium sulfate.     

Internal stress analysis of epoxy adhesively-boned joints based on their thermomechanical properties at cryogenic temperature

Internal stress analysis is essential to structural design of materials applied in cryogenic engineering. In this contribution, thermomechanical properties including dynamic thermomechanical properties and thermal expansion behavior of four epoxy resins, namely the polyurethane modified epoxy resin (PUE), diglycidyl ether of bisphenol A (DGEBA), tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol (TGPAP) were studied by dynamic thermomechanical analysis. Internal stress of the epoxy layer in the bonded joint was calculated based on the thermomechanical properties. Meanwhile, the structure-cryogenic property relationship of epoxy resins were investigated. Results demonstrate that internal stress in the four epoxies bonded joints is 6 ~ 21 MPa at −150°C, and is positively correlated with the average thermal expansion coefficient (CTE) of epoxy resins. TGDDM and TGPAP showed higher retention of lap shear strength both at −196°C and after temperature cycling due to their lower CTE. Morphology of the fractured surface of bonded joints demonstrated that internal stress is responsible for the severe interface failure at −196°C. It reveals that selection of epoxy resins with low CTE is beneficial for designing high-performance epoxy adhesive systems served at cryogenic temperature.     

Synthesis and characterization of diphenylsilanediol modified epoxy resin and curing agent

A series of diphenylsilanediol modified epoxy resins and novel curing agents were synthesized. The modified epoxy resins were cured with regular curing agent diethylenetriamine (DETA); the curing agents were applied to cure unmodified diglycidyl ether of bisphenol A epoxy resin (DGEBA). The heat resistance, mechanical property, and toughness of all the curing products were investigated. The results showed that the application of modified resin and newly synthesized curing agents leads to curing products with lower thermal decomposition rate and only slightly decreased glass transition temperature (T_g), as well as improved tensile modulus and tensile strength. In particular, products cured with newly synthesized curing agents showed higher corresponding temperature to the maximum thermal decomposition rate, comparing with products of DGEBA cured by DETA. Scanning electron microscopy micro images proved that a ductile fracture happened on the cross sections of curing products obtained from modified epoxy resins and newly synthesized curing agents, indicating an effective toughening effect of silicon–oxygen bond.     

Epoxy resins modified by carbon dioxide

The modification of epoxy resins by means of carbon dioxide is presented. The resulting resins contained different amounts of cyclic carbonates (1,3-dioxolane-2-one rings) instead of a part of epoxy groups. The effect of the cyclic carbonate content on viscosity, gel time, peak exotherms, and crosslinking extent of the above mentioned resins was investigated. Mechanical and thermomechanical properties of the modified resins cured with triethylenetetramine have been determined. It was found that heat-distortion temperature, impact resistance, hardness, compressive strength, and lap shear strength of the resins containing cyclic carbonates were higher than those of unmodified ones.     

Failure behavior of adhesively bonded joints with a rubber modified epoxy adhesive under tensile-shear combined cyclic loading

Rubber-modified epoxy adhesives are used widely as structural adhesive owing to their properties of high fracture toughness. In many cases, these adhesively bonded joints are exposed to cyclic loading. Generally, the rubber modification decreases the static and fatigue strength of bulk adhesive without flaw. Hence, it is necessary to investigate the effect of rubber-modification on the fatigue strength of adhesively bonded joints, where industrial adhesively bonded joints usually have combined stress condition of normal and shear stresses in the adhesive layer. Therefore, it is necessary to investigate the effect of rubber-modification on the fatigue strength under combined cyclic stress conditions. Adhesively bonded butt and scarf joints provide considerably uniform normal and shear stresses in the adhesive layer except in the vicinity of the free end, where normal to shear stress ratio of these joints can cover the stress combination ratio in the adhesive layers of most adhesively bonded joints in industrial applications.

In this study, to investigate the effect of rubber modification on fatigue strength with various combined stress conditions in the adhesive layers, fatigue tests were conducted for adhesively bonded butt and scarf joints bonded with rubber modified and unmodified epoxy adhesives, wherein damage evolution in the adhesive layer was evaluated by monitoring strain the adhesive layer and the stress triaxiality parameter was used for evaluating combined stress conditions in the adhesive layer. The main experimental results are as follows: S–N characteristics of these joints showed that the maximum principal stress at the endurance limit indicated nearly constant values independent of combined stress conditions, furthermore the maximum principal stress at the endurance limit for the unmodified adhesive were nearly equal to that for the rubber modified adhesive. From the damage evolution behavior, it was observed that the initiation of the damage evolution shifted to early stage of the fatigue life with decreasing stress triaxiality in the adhesive layer, and the rubber modification accelerated the damage evolution under low stress triaxiality conditions in the adhesive layer.     

Aging and performance of structural film adhesives. I. A comparison of two high-temperature curing,epoxy-based systems

The room temperature aging of two epoxy adhesives, both of which are cured at 177°C and contain the moisture sensitive resin triglycidyl (4-aminophenol), has been examined. It has been found that hydrolysis of this resin is the major cause of reduction in epoxide content during aging. This in turn is largely responsible for the deterioration in the performance, especially at high temperatures, of bonded joints made with aged adhesive. The advantages of using high purity resins in adhesive formulations have been demonstrated.     

Examination of selected synthesis parameters for wood adhesive‐type urea–formaldehyde resins by 13C NMR spectroscopy. III

The varying polymer structures of wood adhesive‐type urea–formaldehyde resins resulting from different formaldehyde/first urea (F/U₁) mole ratios used in the first step of resin manufacture were investigated using ¹³C. As the F/U₁ mole ratio decreased progressively from 2.40 to 2.10 and to 1.80, the viscosity increase due to polymerization during resin synthesis became faster and resulted in decreasing side‐chain branches and increasing free urea amide groups in the resin structure. The resultant UF resins, with the second urea added to an overall F/(U₁ + U₂) of 1.15, showed viscosity decreases when heated with stirring or allowed to stand at room temperature that were also characteristic with the F/U₁ mole ratios used in resin synthesis. The formaldehyde emission levels of particleboards bonded with the freshly made UF resins showed relatively small but similarly characteristic variations. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2800–2814, 2001