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1.
Epoxy adhesive with high underwater adhesion and stability based on low viscosity modified Mannich bases
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A series of Mannich base curing agents were synthesized by using different structured phenols and amines. The phenols were phenol, o‐cresol, and nonylphenol, and the amines were diethylenetriamine, m‐xylylenediamine, and JEFFAMINE D230 polyetheramine. The chemical structures of Mannich bases were confirmed by 1H nuclear magnetic resonance and Fourier transform infrared spectroscopy. The curing agents had low viscosities in the range of 19.9 to 1549 mPa s. The curing behavior of diglycidyl ether of bisphenol A with these curing agents was studied by differential scanning calorimetry. The mechanical properties and thermal properties of the cured epoxies were also investigated and compared. Lap‐shear adhesion in air and underwater was studied by using stainless steel substrates, and the adhesion after ageing in hot water (80 °C) was also investigated. Adhesive cured with phenol modified m‐xylylenediamine showed the highest underwater adhesion around 5.9 MPa, which was comparable to other ones tested in air. In addition, the high adhesive strength was kept after ageing in hot water for 7 days. The structural influence of the curing agents on mechanical property and adhesive performances were discussed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45688. 相似文献
2.
In this investigation, the mechanical properties such as compression, impact, and flexural properties of graphene decorated with graphene quantum dots (GDGQD) epoxy composites with concentration of GDGQD ranging from 0.25 to 1 wt % were studied. Ideal mechanical properties are obtained by systematically varying the filler weight in the epoxy matrix. The morphological studies of GDGQD have been characterized using transmission electron microscope, X-ray diffraction, and Fourier transform infrared technique. The compression, impact, and flexural strengths were enhanced effectively by the GDGQD loading. With the addition of 0.75 wt % of GDGQD, the compressive strength, compressive modulus, flexural strength, and flexural modulus of the composites were improved by 22, 29, 31, and 63%, respectively. Also an improvement in impact strength of 102% for 0.75 wt % GDGQD epoxy sample was also obtained. Examination of fractured test specimens was performed with scanning electron microscope. The enhancement in the mechanical properties is due to the better stress transfer that is attributed by enhanced interfacial bonding between GDGQDs and the epoxy. Using the GDGQD aspect ratio in the two-dimensional randomly oriented filler modified Halpin–Tsai model, the theoretical flexural modulus for the GDGQD/epoxy composites has been established. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48680. 相似文献
3.
Effect of modified phenolic resin on crosslinked network and performances of polyvinyl acetate blending emulsion
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The water‐soluble phenolic resin (PF) and the poly(vinyl alcohol) (PVA) modified phenolic resin (PPF) were synthesized by alkali catalysis method. Both were used as curing agents to blend with the polyvinyl acetate (PVAc) emulsion. The obtained PF, PPF and blending emulsion were characterized by FT‐IR, DSC, DLS, TEM, and viscosity analysis. The thermal stability of latex films was enhanced after blending. When the PF and PPF content was up to 15 wt %, the peel strength of the blending emulsion increased from 17.89 N/25 mm to 21.32 N/25 mm and 23.37 N/25 mm and the shear impact strength were 1.4 and 1.6 times that of unmodified emulsion adhesive, respectively. Moreover, the modification effect of PPF was better than PF due to its tough crosslinked network. Finally, layer cohesion played an increasingly important role in bonding forces with the increment of the PPF content by the glue residue analysis. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46448. 相似文献
4.
In this work, the multiepoxy functional glycidyl ether (GE) modified urea‐formaldehyde (UF) resins were synthesized via a traditional alkaline‐acid process under low formaldehyde/urea (F/U) molar ratio. The synthesized resins were characterized by 13C magnetic resonance spectroscopy (13C‐NMR), indicating that GE can effectively react with UF resins via the ring‐opening reaction of epoxy groups. Moreover, the residual epoxy groups of GE could also participate in the curing reaction of UF resins, which was verified by Fourier transform infrared spectroscopy. The storage stability of GE‐modified UF resins and the thermal degradation behavior of the synthesized resins were evaluated by using optical microrheology and thermogravimetric analysis, respectively. Meanwhile, the synthesized resins were further employed to prepare the plywood with the veneers glued. For the modification on bonding strength and formaldehyde emission of the plywood, the influences of addition method, type, and amount of GE were systematically investigated. The performance of UF adhesives were remarkably improved by the modification of GE around 20–30% (weight percentage of total urea) in the acidic condensation stage during the resin synthesis. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 相似文献
5.
Urea formaldehyde resin with low formaldehyde content modified by phenol formaldehyde intermediates and properties of its bamboo particleboards
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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. 相似文献
6.
Preparation and properties of heat and ultraviolet‐induced bonding and debonding epoxy/epoxy acrylate adhesives
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Heat and ultraviolet (UV)‐induced bonding and debonding (BDB) adhesives were designed and prepared through blending an epoxy resin, diglycidyl ether of bisphenol A (DGEBA) with an epoxy acrylate resin, bisphenol‐A epoxy acrylate resin (BEA). The variation of the chemical structure of DGEBA and BEA in the sequential heat‐ and UV‐curing processes was characterized by Fourier transform infrared spectroscopy (FTIR). The FTIR results indicate that DGEBA and BEA successfully took part in both the heat‐curing and UV‐curing processes. The effects of the mass ratio of BEA to DGEBA, amount of heat‐curing agent, type of diluents, and UV irradiation time on the BDB properties of BDB adhesive were systematically investigated. The results show that the bonding strength increases with the decrease of the mass ratio of BEA to DGEBA and with the increase of the amount of heat‐curing agent in a certain range. The debonding strength decreases with the increase of the mass ratio of BEA to DGEBA. The mass ratio of BEA to DGEBA was set at 10 to ensure the ratio of the bonding strength to debonding strength greater than 10 times. The debonding strength of BDB adhesives also depends on the UV irradiation time, decreasing with the increase of UV irradiation time in a certain range. Based on the FTIR results and the dependence of the bonding and deboning strengths on the reaction conditions, a possible BDB mechanism of BDB adhesive was proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46435. 相似文献
7.
Tetrafunctional epoxy as an all‐purpose modifier for homopolymerized bisphenol A diglycidyl ether
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In some applications, homopolymerized epoxies, which offer better biocompatibility and lower water absorption than amine‐ and anhydride‐cured epoxy, are more preferable; however, using homopolymerized epoxy as matrix in composites still remains a challenge. Herein, homopolymerized bisphenol A diglycidyl ether curing systems with simultaneously improved tensile strength, impact strength, and glass transition temperature (Tg) were achieved by addition of small amounts of tetra‐functional epoxies (TFTEs) with different spacer lengths. Effects of spacer length in TFTE on thermal and mechanical properties were investigated. Results indicated that TFTE with the longest spacer length shows the best mechanical performance. In addition, effects of TFTE loading on thermal and mechanical properties were discussed. Compared with neat bisphenol A diglycidyl ether, addition of 5% tetraglycidyl‐1,10‐bis(triphenylmethane) decane leads to simultaneous improvements in tensile strength, impact strength, and Tg. Effects of thermal cycling on the mechanical properties were also reported. Results suggest that the modified homopolymerized epoxy shows good performances and could be used as matrix materials and possibly in some dental applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46431. 相似文献
8.
Urea‐formaldehyde (UF) resins are prone to hydrolysis that results in low‐moisture resistance and subsequent formaldehyde emission from UF resin‐bonded wood panels. This study was conducted to investigate hydrolytic stability of modified UF resins as a way of lowering the formaldehyde emission of cured UF resin. Neat UF resins with three different formaldehyde/urea (F/U) mole ratios (1.4, 1.2, and 1.0) were modified, after resin synthesis, by adding four additives such as sodium hydrosulfite, sodium bisulfite, acrylamide, and polymeric 4,4′‐diphenylmethane diisocyanate (pMDI). All additives were added to UF resins with three different F/U mole ratios before curing the resin. The hydrolytic stability of UF resins was determined by measuring the mass loss and liberated formaldehyde concentration of cured and modified UF resins after acid hydrolysis. Modified UF resins of lower F/U mole ratios of 1.0 and 1.2 showed better hydrolytic stability than the one of higher F/U mole ratio of 1.4, except the modified UF resins with pMDI. The hydrolytic stability of modified UF resins by sulfur compounds (sodium bisulfate and sodium hydrosulfite) decreased with an increase in their level. However, both acrylamide and pMDI were much more effective than two sulfur compounds in terms of hydrolytic stability of modified UF resins. These results indicated that modified UF resin of the F/U mole ratio of 1.2 by adding acrylamide was the most effective in improving the hydrolytic stability of UF resin. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
9.
A series of bismaleimide-triazine (BT) resins with and without O, O′-diallyl bisphenol A (DABPA) were produced by mixing 2, 2-bis (4-cyanatophenyl) propane (BADCy) and MCBMI (2,6-bis(4-(1-(4-(4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)phenoxy)-3-methylphenyl)-3-oxo-1,3-dihydroisobenzofuran-1-yl)-2-methylphenoxy)benzonitrile). The resins show just one glass-transition temperature (T g) and enhanced flexural properties as well as superior fracture toughness compared with commercial BDM/BADCy system, in which BDM is (N,N′-bismaleimido-4,4′-diphenylmethane). Introduction of DABPA can decrease the curing temperature of bismaleimide-triazine (BT) resins but increase its impact strength. When the mole of DABPA reach up to 1.2, the impact strength was increased by 1.34 times in comparison with BDM/ BADCy system. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 136, 47420. 相似文献
10.
Alejandro Bacigalupe Mariela Fernández Patricia Eisenberg Mariano M. Escobar 《应用聚合物科学杂志》2020,137(37):49086
There is a global concern about the types of adhesives used for the binding of wood particles, most of which include formaldehyde in their formulation. The aim of this work is to study the effect of raw montmorillonite (Mt) particles on blended urea formaldehyde (UF)/soy protein (SP) adhesives for the manufacture of wood particleboards to reduce the use of this carcinogenic component. Rheology showed that Mt does not alter the viscosity of adhesives at high shear rates, so they can be applied by spray. Thermogravimetric analysis/derivative thermogravimetry (TGA/DTG) analysis revealed an enhancement of their thermal stability due to the presence of clay particles. Polymer–Mt interaction was studied by small amplitude X-ray scattering and scanning electron microscopy. According to these results, the exfoliated structure of the clay particles was achieved. Wood particleboards were manufactured with UF/SP/Mt adhesives in order to study their mechanical properties. The three-point bending test showed that Mt particles improved the modulus of both rupture and elasticity. UF/SP/Mt resins proved to be a prominent product for the development of environmentally friendlier particleboards with desirable mechanical properties. 相似文献
11.
We obtained lignin‐based wood adhesives satisfying the requirements of relevant international standards for the manufacture of wood particleboard. These were based on two different low‐molecular‐mass lignins. These lignin‐based wood adhesives did not use any formaldehyde in their formulation; formaldehyde was substituted with a nonvolatile nontoxic aldehyde, namely, glyoxal. The last formaldehyde present, contributed by a fortifying synthetic phenol–formaldehyde resin, was also eliminated by the substitution of the phenol–formaldehyde resin with a natural, vegetable polyflavonoid tannin extract to which no aldehyde was added. This substitution brought the total content of natural material up to 80 wt % of the total adhesive. The adhesives yielded good internal bond strength results of the panels, enough to pass relevant international standard specifications for interior‐grade panels. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
12.
Acrylic monomers and free‐radical initiators were dispersed in an aqueous urea–formaldehyde (UF) suspension and polymerized in situ to afford a suspension containing 5 wt % thermoplastic (5 g of thermoplastic/100 mL of suspension). The viscosity of the thermoplastic‐modified UF suspension (65 wt % solids at 25°C) ranged from 240 to 437 cP versus 121 cP for the unmodified UF control. Wood‐flour composites (sugar maple and 50 wt % adhesive) were prepared with thermoplastic‐modified UF suspensions and cured with the same cycle used for the composites prepared with the unmodified UF adhesive (control). The effect of the thermoplastic‐modified UF adhesive was evaluated on the notched Izod impact strength and equilibrium moisture uptake of the wood‐flour composites. The notched Izod impact strength of the composites prepared with modified UF adhesives increased by as much as 94% above that of the control. The increase depended on the initiator and the monomer composition. The modification affected the equilibrium moisture uptake and rate of moisture uptake in the wood‐flour composites. Preliminary results for particleboard prepared with 10 wt % modified UF adhesive (5% thermoplastic in the UF resin) and unoptimized cure conditions confirmed a significant effect of the thermoplastic modification on both the internal‐bond strength and thickness swelling of the particleboard. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
13.
Yawen Huang Quanli Zhang Qiuxia Peng Huan Hu Hongtao Yu Junxiao Yang Lili Liu 《应用聚合物科学杂志》2019,136(20):47465
Organosilicon resins have been demonstrated to be promising materials for low-dielectric-constant (low-k) related applications. In this study, we proposed a method to further reduce the dielectric constant (k) value of organosilicon resins with [1,1-dimethyl,1-(4′-benzocyclobutenyl)silyl] cyclotetrasiloxane (BCB-D4) as a building block. This building block was prepared by the hydrosilylation reaction of tetravinyl cyclotetrasiloxane with dimethyl–benzocyclobutene–silane. The reaction of benzocyclobutene on BCB-D4 by bulk polymerization in modules directly produced a highly crosslinked resin (poly{[1,1-dimethyl,1-(4′-benzocyclobutenyl)silyl] cyclotetrasiloxane) [poly(BCB-D4)]). Poly(BCB-D4) exhibited a low k of about 2.70; this value was greatly lower than the k (~3.0) of conventional benzocyclobutene–organosilicon resins obtained by the curing of linear polysiloxane. The low k was possibly due to the porous structure, which was constructed from multifunctionalized and cyclic building blocks. In addition, poly(BCB-D4) also exhibited a relatively high modulus (5.0 GPa) without a sacrifice in the thermal resistance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47465. 相似文献
14.
The characterization of film adhesives is challenging because they required freezer storage, contain an inseparable filler—thermoplastic knit or fiber‐reinforcement, and are heat activated systems with a pre‐cure and unknown chemistry. A testing protocol that eliminates these sources of error is proposed. This study presents a method to generate time–temperature‐transformation (TTT) diagrams of epoxy film adhesives via differential scanning calorimetry (DSC). Non‐isothermal and isothermal DSC scans are used to capture the reaction and the glass transition temperature. The use of an initial fast ramp—up to 500 K/min—in the isothermal scans is explored for the first time. This technique shows the potential to produce a quasi‐isothermal cycle, eliminating the loss of data in the initial stage of the reaction. The total heat released, the activation energy, and the fractional kinetic parameter, are estimated via model‐free methods. The Kamal–Sourour model and the formal kinetic model are fit to model the rate of cure. The simplest model that accurately captures the reaction, a parallel two‐step model, A , is outlined. The glass transition temperature is modeled via DiBenedetto's equation to include the diffusion‐controlled mechanism. The TTT‐diagrams of two commercial adhesives, DA 408 and DA 409, are shown with an analysis of processing optimization. The use of quasi‐isothermal scans with initial fast ramps combined with the correction for filler, moisture, and pre‐curing history can be applied to characterize fast curing thermosets, complex B‐stage resins, and thermosetting composites. The modeling results can also be used in numerical studies of residual stresses and dimensional stability in the manufacturing of thermosetting composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45791. 相似文献
15.
The addition of small percentages of Na+‐montmorillonite (NaMMT) nanoclay appears to improve considerably the performance of thermosetting urea‐formaldehyde (UF) resins used as adhesives for plywood and for wood particleboard. X‐ray diffraction (XRD) studies indicated that NaMMT loses the periodic atomic structure when mixed in small proportions in the acid‐curing environment characteristic of the curing of UF resins. This can be interpreted as becoming exfoliated under such conditions. The partly crystalline structure of the ordered zones of the UF resins is maintained but at a slightly lower level. Differential scanning calorimetry (DSC) indicated that NaMMT has an accelerating effect on the curing of the UF resin. It also appears to lead to a more controlled rate of crosslinking implying a more regular hardened network. The influence of NaMMT addition was particularly noted in plywood by the increase in water resistance of the UF‐bonded panel. In the case of wood particleboard even the dry internal bond strength of the panel, a direct indication of the performance of the resin, improved with small additions of NaMMT. A hypothesis and model of the reasons why such improvement to the performance of UF resins by addition of nanoclay should occur has been presented. This is based on the application of percolation theory to the networking capability of the clay nanoplatelets. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
16.
John Puentes Nora Catalina Restrepo‐Zapata Alexander Chaloupka Lukas J. L. Duddleston Natalie Rudolph Tim A. Osswald 《应用聚合物科学杂志》2017,134(42)
Three major factors decrease the accuracy of the cure measurement in standard‐isothermal testing using differential scanning calorimetry (DSC). First, cure occurs during the heating step. Second, data are lost during the stabilization period between the dynamic and isothermal step. Third, the baseline selection requires a modification to the protocol. An alternative, which is explored in this study, is the use of fast ramps, which decrease the heating time, but this has been avoided due to overshoot that occurs between the dynamic and isothermal step, which is troublesome for systems with autocatalytic kinetics. By mitigating these factors, a quasi‐isothermal protocol was developed. Therefore, more complete cure kinetics were captured with the implementation of fast DSC to decrease the ramp time and through the optimization of furnace parameters to decrease stabilization time and temperature overshoot. The data suggested this quasi‐isothermal analysis more accurately measured the isothermal curing kinetics of a commercial epoxy adhesive at 110, 115, and 120 °C for fast ramps of 175, 350, and 500 K/min compared to the traditional ramp of 5 K/min. The enthalpy spike at the dynamic to isothermal transition remains an issue; however, an empirical shift can be used to compensate for the enthalpy signal lag. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45425. 相似文献
17.
Lap shear strength and thermal stability of diglycidyl ether of bisphenol a/epoxy novolac adhesives with nanoreinforcing fillers
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Nanoreinforcing fillers have shown outstanding mechanical properties and widely used as reinforcing materials associated to polymeric matrices for high performance applications. In this study, a series of multiwalled carbon nanotubes (MWCNTs)‐, nano‐Al2O3‐, nano‐SiO2‐, and talc‐reinforced epoxy resin adhesives composites were developed. The influence of different types and contents of nanofillers on adhesion, elongation at break, and thermal stability (under air and nitrogen atmospheres) of diglycidyl ether of bisphenol A (DGEBA)/epoxy novolac adhesives was investigated. A simple and effective approach to prepare adhesives with uniform and suitable dispersion of nanofillers into epoxy matrix was found to be mechanical stirring combined with ultrasonication. Transmission electron microscopic and scanning electron microscopic investigations revealed that nanofillers were homogeneously dispersed in epoxy matrix at optimized nanofiller loadings. Adhesion strength was measured by lap shear strength test as a function of nano‐Al2O3 and MWCNTs loadings. The results indicated that the lap shear strength was significantly increased by about 50% and 70% with addition of MWCNTs and nano‐Al2O3 up to a certain level, respectively. The highest lap shear strength was reached at 1.5 wt % of nano‐Al2O3 loading. MWCNTs at all loadings (except 3 wt %) and nano‐Al2O3 have enhanced onset of degradation temperature and char yield of the adhesives. By combined incorporation of 0.75 wt % nano‐Al2O3 and 0.75 wt % MWCNTs into the epoxy novolac/DGEBA blend adhesives a synergistic effect was observed in the thermal stability of the adhesives at high temperatures (800°C). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40017. 相似文献
18.
Pattoorpady Krishnan Sandhya M. S. Sreekala Guijun Xian Moothetty Padmanabhan Nandakumar Kalarikkal Sabu Thomas 《应用聚合物科学杂志》2020,137(40):49211
Graphene oxide was reduced (RGO) by naturally abundant potato starch and incorporated in phenol formaldehyde resin (PF). The PF/RGO nanocomposites were successfully fabricated by the combination of solution processing and compression molding. Here, nanocomposites composed of 0.05 wt% to 1 wt% RGO were prepared. The incorporation of RGO into the PF matrix was significantly affecting the dynamic mechanical characteristics of the nanocomposites such as storage and loss modulus and tan δ. The degree of entanglement (N), effectiveness of filler (βf ), reinforcement efficiency factor (r), cross-link density (vc ), and adhesion factor (A) were evaluated from the modulus values. Besides, the phase behavior of the nanocomposites was analyzed with help of Cole–Cole plot. The electrical properties of the nanocomposites have been studied concerning change in filler loading and frequency. The dielectric constant (ε′), dielectric loss (ε″) and conductivity were increased with increase in wt% of filler for the entire range of frequencies (20 Hz to 30 MHz) and the results showed that the electrical conductivity of the nanocomposites can be explained by percolation theory. The Maxwell-Garnet model was employed to calculate the theoretical dielectric constant of PF/RGO nanocomposites. 相似文献
19.
Iclal Avinc Akpinar Ahmet Gürses Kürşat Gültekin Hamit Akbulut Adnan Ozel 《The Journal of Adhesion》2018,94(11):847-866
ABSTRACTIn recent years, findings in nanoscience and nanotechnology have deeply influenced many disciplines including the material and mechanical sciences. Polymers including nanostructures have attracted attention as their adoptions in general engineering composites have yielded efficient results. In this study, three different two-component (epoxy-hardener) adhesives were doped with graphene nanoplatelets, graphene oxide nanoplatelets, carbon nanotube, and fullerene C60 at three different rates (0.5%, 1%, and 2% by weight) and the mechanical and thermal properties of the nanocomposite adhesives were examined. The nanocomposite adhesives’ mechanical properties were analyzed via tensile tests and thermal properties were analyzed via Differential Scanning Calorimeter (DSC) thermograms and Fourier Transform Infrared Spectroscopy (FT-IR) spectra. Results showed that doping nanostructures improve the stress-strain capacity of the adhesives. Both mechanical and thermal properties of the nanocomposite adhesives seem to change depending on the amount of nanostructure. Additionally, DSC and FT-IR curves showed an agreement with these improvements in the adhesives’ mechanical properties. 相似文献
20.
Ruya Isam Bakr Albaker Suheyla Kocaman Mustafa Esen Marti Gulnare Ahmetli 《应用聚合物科学杂志》2021,138(31):50770
In this study, chemically modified walnut shells (WS) were used as the filling material for synthesis of bio-based epoxy composites and added to the matrix at varied mass ratios (10%–50%). The shells were initially treated with alkali and then modified with three different organic acids (citric acid [CA], oxalic acid [OA], and formic acid [FA]). The WS were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM)/energy-dispersive X-ray spectroscopy (EDX) and thermo gravimetric analyzer. The SEM and X-ray diffraction were employed to observe the morphology of the composites. The influences of acid type and WS percentages on the mechanical, thermal and water sorption properties were investigated. The maximum tensile strength (124.8 MPa) was obtained with CA-treated shells (CA-WS) and followed by OA-treated shells (OA-WS) (117 MPa) and FA-treated shells (FA-WS) (96.5 MPa). Acid modification had a positive effect on Young's modulus as that of epoxy resins increased by 5.45%–50.91%. The treatment did not significantly affect hardness. The optimum amount of modified shells in the composites was found to be 20 wt%. Water sorption values changed in the range of 2.78%–3.42% for composites with 20 wt% WS and observed to increase with the filler amount in the composite. However, this trend and the slight decrease in thermal properties are not critical obstacles for the use of modified WS in the manufacture of inexpensive epoxy- and bio-based eco-friendly products. 相似文献