Curing Behavior of Wood Adhesives Under High Steam Pressure

Steam-injection pressing is a recent development for manufacturing wood products. The curing mechanism and behavior of wood adhesives during steam-injection heating and hot-platen heating may cause differences in both chemical and physical aspects. The curing of wood adhesives under high steam pressure using an especially designed reaction cell is discussed. The adhesives used in this study were phenol-formaldehyde (PF), urea-formaldehyde (UF), melamine-formaldehyde (MF), and isocyanate (IC) resins. At different curing times, the heating temperature (steam pressure) applied to cure the adhesives was 160°C (6 kgf/cm²). Results were examined by analytical methods using FR-IR, ¹³C-NMR, dynamic mechanical analysis and solvent extraction. (1) By steam-injection heating, PF resin immediately cured to some degree in a few minutes and maintained an equilibrium situation. In this case, the reaction was accompanied by the disappearance of the ether structure. (2) In UF resin, results from IR data clarified different reactions between hot-platen heating and steam-injection heating. During steam-injection heating, as heating time increased, UF resin returned to its liquid state under the influence of hydrolysis. (3) MF resin was almost cured under steam-injection in a short heating time compared with hot-platen heating. (4) IC resin foamed and cured in a short heating time under steam-injection. It was proved that steam-injection heating was more effective than by hot-platen heating for IC resin.     

Characteristics of epoxy resin cured with in situ polymerized curing agent

In order to improve the heat resistance of a cured epoxy resin together with reducing the viscosity of the resin composition, an epoxy resin was cured with a curing agent formed from the radical copolymerization of vinyl monomers during the cure process of the epoxy resin. N-phenylmaleimide and p-acetoxystyrene were used as vinyl monomers of the curing agent. The epoxy resin was cured by the insertion reaction of the ester group of the in situ polymerized curing agent and the epoxy group of the epoxy resin. In the cure system of the epoxy and the phenol resins, reduction of the viscosity of the resin composition was achieved by replacing some or all of the phenol resin with these monomers. When all phenol resins were replaced by these monomers, the viscosity of resin composition (0.01 Pa s at 70 °C) decreased by about 1/2000 compared with that of the system with only phenol resin (21 Pa s at 70 °C). The glass transition temperature (T_g) of the cured resin with no phenols was 174 °C, an improvement of 17 °C compared with that of the system cured with only phenol resin. The flexural strength of the new resins remained unchanged.     

NMR Imaging of the Interfaces of Epoxy Adhesive Joints

Nuclear magnetic resonance imaging (NMRI) is used to study epoxy adhesive bonded structures at a proton resonance frequency of 300 MHz. Oligomeric and almost pure monomeric diglycidyl ethers of bisphenol-A, triethylenetetramine and xylene representing typical raw materials of epoxy adhesives are imaged at 25 and 50°C with varying repetition times to optimize measurement conditions for the adhesives. NMR images with good signal-to-noise ratios from the liquid epoxy adhesives are obtained at 50°C using the shortest possible echo times and a repetition time of 1 s. Chemical shift images of the glue-lines are presented and their possible uses in adhesive studies are discussed. The use of NMRI to detect heterogenous resin/resin and resin/curing agent mixtures is demonstrated. A non-invasive glue-line analysis is made of an aluminium/epoxy/aluminium sample with a model debonding by recording cross-sectional NMR images and a proton shadowgram.     

NOTE: THERMALLY REMOVABLE EPOXY ADHESIVES INCORPORATING THERMALLY REVERSIBLE DIELS-ALDER ADDUCTS

Thermally reversible adhesives are prepared through the reaction of aliphatic diamines and a diepoxy compound containing two Diels-Alder adducts. The diepoxy compound is formed via the Diels-Alder reaction between two epoxy-containing furans and a bismaleimide. The adhesive displays a T g of -40°C and a constant shear modulus up to approximately 90°C. At temperatures exceeding 90°C the retro Diels-Alder reaction occurs, which leads to a significant loss in modulus. The loss of modulus is reversible with temperature. A thermally reversible adhesive is proposed based upon the loss of modulus at an elevated temperature, i.e., adhesives bonds are easily broken at elevated temperature where the modulus is low.     

Effect of curing systems and temperatures on the activity of retarder in natural rubber mixes

The effect of vulcanization temperature (150° and 180°C) on the structure and technical properties of gum natural rubber vulcanizates with four different 2-(morpholinodithio)-benzothiazole (MDB) — sulphur ratios in presence of N-(cyclohexyl thio)-phthalimide (CTP, 0.5 phr) has been determined at the respective optimum cure times. The influence of curing system, temperature and retarder on (a) the chemical crosslink density, (b) the distribution of crosslink types, (c) the extent of sulphidic main chain modification and (d) the zinc sulphidic formation have been investigated. The network results have been correlated with the technical properties. Increasing the cure temperature by 30°C (from 150° to 180°C) does not alter the activity of CTP. It is effective in all curing systems, but effectiveness was maximum in the conventional system. At 0.5 phr level, CTP caused reduction in most technical properties.     

Prevention of Hydrosilation Cure Inhibition in a Polysiloxane Adhesive by Surface Oxidation

For a variety of reasons epichlorohydrin-ethylene oxide (ECO)-based compounds, in the form of rain erosion boots or sleeves, are bonded to aircraft radomes using a hydrosilation-cured RTV polysiloxane adhesive. Unfortunately, cure of the adhesive can be completely inhibited by unreacted vulcanizing agent and/or ECO cure by-products. We have earlier shown that this inhibition can be prevented by treating the ECO surface with hydrogen peroxide to oxidize the hydrosilation catalyst poisons to a harmless state. In this study we have used spectroscopic techniques to monitor the hydrosilation reaction kinetics and in turn to identify the poison, define the poisoning level and monitor the poison removal by hydrogen peroxide treatment. The degree of poison removal is also correlated with adhesive bond strength using a 180°; peel test. The critical poison in the system was excess ECO vulcanizing agent which can be completely removed from the surface using a 30 vol. % H₂O₂ treatment for 30 minutes as long as the initial vulcanizing agent concentration is 1 p.p.h. or less.     

DTA characterisation of three types of Al2O3SiO2 gels made from TEOS-Al (OBu)3 mixture with variation of water

Mixtures of TEOS and Al (OBu)₃ had been hydrolysed by varying the water contents at a fixed acid concentration. This led to the formation of three different kinds of gels. Diphasic gel formed when excess of water was used, which transformed to mullite at 1320 °C in exothermic reaction. When the amount of water content was reduced, the resultant monophasic gel completed its mullitization at lower temperatures from an amorphous aluminosilicate phase and cubic mullite by two paths at 1150 °C and 1250 °C exothermic reactions, respectively. When less water is used, the monophasic gel converted directly to tetragonal mullite at 980 °C in exothermic reaction. Thus, the variation of water contents during the gelation caused great variations in the course of mullitization processes.     

Synthesis, cure kinetics and thermal properties of the 2,7-dihydroxynaphthalene dicyanate

The novel dicyanate ester resin containing the naphthalene ring (DNCY) was synthesized from 2,7-dihydroxynaphthalene and cyanogen bromide by two-step method. The monomer of DNCY was characterized by FT-IR, ¹H NMR, ¹³C NMR and elemental analyses (EA). The cure behavior of DNCY was studied by means of nonisothermal DSC, and the kinetics parameters were determined by the Kissinger method. The thermal properties of DNCY resin were studied by thermal degradation analysis at a heating rate of 10 °C min⁻¹ both in N₂ (thermal stability) and in air (thermal-oxidative stability). The DNCY resin showed excellent thermal stability, compared with that of bisphenol A dicyanate (BACY) resin, which could be demonstrated by the extensional onset temperature (435.8 °C), the temperature of maximum weight loss rate (450.3 °C) and the percentage char yields at 700 °C (60.5%) in N₂, and thermal-oxidative stability, which could be demonstrated by the extensional onset temperature (435.4 °C), the first temperature of maximum weight loss rate (450.7 °C), the second temperature of maximum weight loss rate (580.0 °C) and the temperature of complete degradation (704.4 °C) in air. The DNCY resin exhibited higher T_g and thermal degradation temperature than BACY resin.     

不饱和聚酯树脂微乳液的快速固化研究

探讨了过氧化物 (过氧化甲乙酮、过氧化氢、叔丁基过氧化氢、异丙苯过氧化氢 ) /抗坏血酸组成的氧化 -还原引发聚合体系对磺酸盐不饱和聚酯树脂及其油包水型微乳液的固化特性。结果表明 :磺酸盐不饱和聚酯树脂的凝胶时间和固化时间都比相应的微乳液长。 4种过氧化物中 ,过氧化氢的常温引发聚合反应最快 ,能使微乳液 30s内凝胶 ,7min内固化 ,达到了快速固化的目的     

Ignition of methanol partial oxidation over supported platinum catalyst

Supported platinum catalysts were prepared by precipitation of H₂PtCl₆ on powders of different metal oxides. Catalytic activity of the prepared catalysts was tested with reaction of partial oxidation of methanol (POM) for hydrogen production. Most of the prepared catalysts can ignite POM at the ambient temperature. The conversion of methanol and the selectivity of hydrogen and carbon monoxide, however, increased with the reaction temperature and varied with the kind of support and platinum loading. A 1 wt% Pt/ZnO catalyst exhibited optimized methanol conversion and selectivity at a low reaction temperature of 150 °C. The reactor may reach this temperature within 2 min after a start of the exothermic reaction.     

An investigation of the thermal stability and sulphur tolerance of Ag/γ-Al2O3 catalysts for the SCR of NOx with hydrocarbons and hydrogen

The sulphur tolerance and thermal stability of a 2 wt% Ag/γ-Al₂O₃ catalyst was investigated for the H₂-promoted SCR of NO_x with octane and toluene. The aged catalyst was characterised by XRD and EXAFS analysis. It was found that the effect of ageing was a function of the gas mix and temperature of ageing. At high temperatures (800 °C) the catalyst deactivated regardless of the reaction mix. EXAFS analysis showed that this was associated with the Ag particles on the surface of the catalyst becoming more ordered. At 600 and 700 °C, the deactivating effect of ageing was much less pronounced for the catalyst in the H₂-promoted octane-SCR reaction and ageing at 600 °C resulted in an enhancement in activity for the reaction in the absence of H₂. For the toluene + H₂-SCR reaction the catalyst deactivated at each ageing temperature. The effect of addition of low levels of sulphur (1 ppm SO₂) to the feed was very much dependent on the reaction temperature. There was little deactivation of the catalyst at low temperatures (≤235 °C), severe deactivation at intermediate temperatures (305 and 400 °C) and activation of the catalyst at high temperatures (>500 °C). The results can be explained by the activity of the catalyst for the oxidation of SO₂ to SO₃ and the relative stability of silver and aluminium sulphates. The catalyst could be almost fully regenerated by a combination of heating and the presence of hydrogen in the regeneration mix. The catalyst could not be regenerated in the absence of hydrogen.     

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.     

Simultaneous production of hydrogen and carbon nanostructures by decomposition of propane and cyclohexane over alumina supported binary catalysts

Nano-scale, binary, 4.5 wt.% Fe–0.5 wt.% M (M = Pd, Mo or Ni) catalysts supported on alumina have been shown to be very effective for the decomposition of lower alkanes to produce hydrogen and carbon nanofibers or nanotubes. After pre-reduction at 700 °C, all three binary catalysts exhibited significantly lower propane decomposition temperatures and longer time-on-stream performances than either the non-metallic alumina support or 5 wt.% Fe/Al₂O₃. Catalytic decomposition of propane using all three catalysts yielded only hydrogen, methane, unreacted propane, and carbon nanotubes. Above 475 °C, hydrogen and methane were the only gaseous products. Catalytic decomposition of cyclohexane using the (4.5 wt.% Fe–0.5 wt.% Pd)/Al₂O₃ catalyst produced primarily hydrogen, benzene, and unreacted cyclohexane below 450 °C, but only hydrogen, methane, and carbon nanotubes above 500 °C. The carbon nanotubes exhibited two distinct forms depending on the reaction temperature. Above 600 °C, they were predominantly in form of multi-walled nanotubes with parallel walls in the form of concentric graphene sheets. At or below 500 °C, carbon nanofibers with capped and truncated stacked-cone structure were produced. At 625 °C, decomposition of cyclohexane produced a mixture of the two types of carbon nanostructures.     

Changes in hydrogen utilization with temperature during direct coal liquefaction

A method for quantitative measurement of the hydrogen utilized in different modes of reaction has been applied to hydroliquefaction reactions at temperatures ranging from 375 to 450 °C. The analytical approach is capable of differentiating hydrogen utilized in hydrogenation reactions from that used in bond scission chemistry (hydrogenolysis). The hydrogenolysis reactions result in breakdown of the coal matrix, formation of light hydrocarbon gas and elimination of organic heteroatoms. The results indicate that in this small continuous reactor, operated at 13.8 MPa (2000 psig) H₂, little net chemical activity of hydrogen occurs at 375 °C. However, at 400 °C, the slurry has been hydrogenated significantly with little net hydrogen incorporation. At 450 °C comparable amounts of hydrogen are consumed in gas generation, heteroatom removal, hydrogenation and matrix breakdown, with large net hydrogen incorporation. These results indicate that at temperatures below the thermolysis threshold of 400 °C, significant internal hydrogen redistribution occurs in the slurry. At higher temperatures, a more conventional hydroliquefaction chemistry involving significant bond cleavage and aromatization is indicated. This approach to analysis of hydrogen utilization requires integration of a variety of analytical data. The uncertainties in these data and their impact on the resultant utilization profile are discussed.     

Mode I fracturing properties of epoxy bonding paste

The wedge-splitting method by Tschegg was applied for the investigation of mode I fracture behavior of epoxy-based adhesives. Specific fracture energy and notch tensile strength of “traditional” thickened laminating resin were measured between −40 and +45 °C and compared to those of four new trial compounds. The adhesives in bulk were investigated as well as the interfaces between these adhesives and glass fiber-reinforced plastic. The wedge-splitting method has turned out suitable for epoxy resin. The quality of thickened laminating resin was not reached by the new trial compounds. Adherend pre-treatment with laminating resin and peel ply improved interfacial properties.     

酚醛改性苯并(噁)嗪树脂耐烧蚀材料的研究

对不同组成苯并口恶嗪/酚醛共混树脂体系进行了研究,内容包括共混树脂的反应动力学参数计算、共固化机理、热分解动力学以及耐烧蚀性能等。结果表明:酚醛与苯并口恶嗪树脂共混后可以改变苯并口恶嗪的固化机理,酚醛树脂的加入使口恶嗪分子由热开环变为活泼氢开环,在较低温度下就可以反应,降低了固化反应温度。同时共混树脂可以使固化过程收缩率和小分子挥发物比传统的酚醛树脂低,可以减少烧蚀试样的表面裂纹,致密的碳化层具有一定附着强度,提高了共混树脂烧蚀性能。该共混体系可以作为宇航领域中1种性能优良的耐烧蚀树脂体系。     

The preparation and performance of high-temperature adhesives for graphite bonding

Two kinds of high-temperature adhesives (HTAs) were prepared. One was composed of phenol-formaldehyde (PF) resin and boron carbide (PF+B₄C), the other was composed of PF resin, B₄C and fumed silica (PF+B₄C+SiO₂). Graphite materials were bonded by the above adhesives and heat-treated at temperatures ranging from 200 to 1500 °C. The joining strength was tested at room temperature. The results show that the graphite joints exhibit satisfactory bonding strength and that ceramics fillers show a marked property modification effect. The strength of graphite joints bonded by PF+B₄C and PF+B₄C+SiO₂ adhesive and treated at 1500 °C are 9.3 and 17.1 MPa, respectively. The property modification mechanism of ceramics fillers is also discussed in this paper. A strong chemical bonding force is introduced at the bonding interface and the volume shrinkage is restrained, which can be responsible for the good adhesive properties of HTAs for graphite bonding.     

Cure kinetics of aqueous phenol‐formaldehyde resins used for oriented strandboard manufacturing: Effect of wood flour

The effect of wood flour on the cure kinetics of commercial phenol‐formaldehyde resins used as oriented strandboard face and core adhesives was studied using differential scanning calorimetry. The wood flour did not change the cure mechanism of the face resin, but lowered its cure temperature and activation energy and increased its cure reaction order. For the core resin (CR), the wood flour lowered the onset cure temperature, and caused separation of the addition and condensation reactions involved in curing of CR. Compared with neat CR, the addition reaction of CR/wood mixture also followed an nth‐order reaction mechanism but with a lower reaction order, while the condensation was changed from an autocatalytic reaction to an nth‐order one. The addition reaction happened at temperatures lower than 90°C, and the condensation reaction was dominant at temperatures higher than 110°C. The proposed models fitted the experimental data well. Relationships among cure reaction conversion (cure degree), cure temperature, and cure time were predicted. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3774–3781, 2006     

Effects of Loading Rate and Temperature on the Mechanical Properties of Structural Adhesives Containing a Carrier

The viscoelastic related properties of four structural adhesives were studied in their bulk form. All four adhesives were based on rubber-toughened epoxy resin with a thermoplastic carrier. Two of the adhesives were commercial film adhesives (120°C curing systems) and the other two were formulated by us from commercially available constituents. The first formulation is a high-temperature-curing system based on cyclo-aliphatic resin and anhydride hardener, toughened with carboxy-terminated butadiene elastomer. The second self-prepared formulation is a special room-temperature-curing adhesive for elevated temperature service, based on a blend of trifunctional and tetrafunctional expoxies cured with triethylene tetramine toughened with amine-terminated butadiene elastomer. The latter formulation was also prepared, in addition to the carrier-containing composition, without the thermoplastic carrier.

As expected for viscoelastic materials, it was found that the yield stress and modulus decreased with temperature. The rate of loading had a pronounced effect on the yield stress which increased with increasing loading rates, and a negligible influence on the modulus. The rate-temperature effects on the yield stress were shown to obey the superposition as described by Eyring's theorem of viscosity. Consequently, the activation energy and activation volume were determined. The high-temperature-curing adhesives comprising a carrier exhibited higher activation energies compared with the room-temperature-curing formulation and other epoxy adhesives cured with aliphatic amines or polyamides reported in the literature.     

UV-Curable Transparent Adhesives for Fabricating Precision Optical Components

UV-curable transparent epoxy adhesives have been specifically developed for the fabrication of optical communictions precision devices. The newly developed adhesives using cylohexane type fluoro-epoxy as the base resin and speherical quartz filler have extremely low volume shrinkage of 1.2% during curing and the cured adhesives have low thermal expansion coefficient of less than 2 × 10^-5/°C. Sheets of the adhesives are colorless and transparent to visible light because the refractive index of the epoxy matrix resin is matched to that of the quatz filler. These highly transparent adhesives can be cured to a depth of more than 5 mm by using 10 mW/cm² UV-irradiation for 30 min. They also have high adhesive strength and good durability. Therefore, they can be used in the fabrication of optical components that require submicron positioning accuracy.