Preparation and properties of crosslinkable waterborne polyurethanes containing aminoplast

In order to improve the water swelling, thermal/mechanical and adhesion properties of waterborne polyurethane (WBPU), a series of the crosslinkable WBPUs containing hydrophilic ionic component, dimethylol propionic acid (20 mole%), were prepared by in-situ polymerization using a cross-linker hexakis (methoxymethyl) melamine (HMMM). Effects of the HMMM content (2, 4, and 6 wt%) and curing temperature on these properties of the crosslinked WBPUs samples were investigated. All properties were found to increase with increasing HMMM content. It was found that the optimum curing temperature of the WBPU films and adhesives was near 120°C, which was not dependent on the HMMM content.     

Properties of waterborne polyurethane (WBPU) coatings: Effect of alkyl chain length of tertiary amines of carboxylic acid salt groups

Waterborne polyurethane (WBPU) dispersions were prepared via a pre-polymer process using 4,4-dicyclohexylmethane diisocyanate (H₁₂MDI), poly(tetramethyleneoxideglycol) (PTMG), 2,2-dimethylol propionic acid (DMPA), ethylene diamine (EDA), and tertiary amines (TAs) with varying amounts of DMPA and TAs. Three TAs with different alkyl chain lengths were used to neutralize the DMPA carboxylic group: N,N-dimethylbutylamine (DMBA, C4), N,N-dimethylhexylamine (DMHA, C6), and N,N-dimethyloctylamine (DMOA, C8). The structures of the synthesized WBPUs were determined via FT-IR and ¹H NMR spectroscopic techniques. The effects of DMPA and TA content and the TA alkyl chain length on stability of dispersions and properties such as water swelling (%), glass transition temperature (T _g ), tensile strength, binding energy and adhesive strength were investigated. The initial adhesive strength of the intact coatings increased with increasing DMPA and TA content and increasing alkyl chain length of TA. However, after immersion of the coatings in water, the adhesive strength decreased. The maximum adhesive strength under water was observed at a DMPA content of 20.20 mol% with 5.30 wt% DMOA, which has the longest alkyl chain.     

Preparation and properties of waterborne polyurethanes based on triblock glycol (CL)4.5-PTMG-(CL)4.5 for water vapor permeable coatings: Effect of soft segment content

A series of waterborne polyurethanes (WBPU) were prepared from 4,4-dicyclohexylmethane diisocyanate (H₁₂MDI), 2,2-bis(hydroxylmethyl) propionic acid (DMPA), ethylenediamine (EDA), triethylamine (TEA), and triblock glycol [TBG, (ε-caprolactone)_4.5-poly(tetramethylene ether) glycol (MW=2000)-(ε-caprolactone)_4.5: (CL)_4.5-PTMG-(CL)_4.5, MW=3000] as a soft segment. Two melting peaks of TBG at about 14°C and 38°C were observed indicating the presence of two different crystalline domains composed of CL and PTMG dominant component. The effect of soft segment content (60–75 wt%) on the colloidal properties of dispersion, and thermal and mechanical properties of WBPU films, the water vapor permeability (WVP) and water resistance (WR) of WBPU-coated Nylon fabrics, and the adhesive strength of WBPU-coated layer and Nylon fabrics was investigated. As soft segment contents increased, the water vapor permeability of WBPU-coated Nylon fabrics increased from 3615 to 4502 g/m²day, however, the water resistances decreased from 1300 to 500 mmH₂O.     

Mechanical properties of semi-interpenetrating polymer network hydrogels based on poly(2-hydroxyethyl methacrylate) copolymer and chitosan

Semi-interpenetrating polymeric network (semi-IPN) hydrogels based on poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(2-hydroxyethyl methacrylate-co-sodium methacrylate) [P(HEMA-co-SMA)], and chitosan with different molecular weights were prepared by crosslinking with ethylene glycol dimethacrylate (EGDMA) and poly(ethylene glycol) diacrylate (PEGDA) and their gelation time, water content, mechanical properties, and morphology were investigated. In consideration of the influence of the molecular weight of chitosan, there is no big difference in the water content, while tensile properties and compressive modulus increased as the molecular weight of chitosan increased. The water content increased and tensile properties and compressive modulus decreased with increasing SMA concentration. Considering the effect of the crosslinking agent, PEGDA had higher water content and lower tensile and compressive moduli than EGDMA. It is suggested that PHEMA/chitosan and P(HEMA-co-SMA)/chitosan semi-IPN hydrogels with different structures and physical properties can be prepared depending on the molecular weight of chitosan, the copolymerization with SMA, and the crosslinking agent type.     

Laterally crosslinked polyurethane copolymers with polycarbonate as a soft segment

The polyurethane (PU) copolymer was laterally crosslinked with an extra MDI, in which a more rigid polycarbonatediol replaced the conventional poly(tetramethyleneglycol) as a soft segment. What is the impact of the possible molecular interaction between polycarbonate soft segments and lateral crosslinking. The structural change after crosslinking and the impact of new soft segment were followed by infrared spectra, crosslink density, UV-VIS spectra, and relative viscosity. The tensile stress could improve as much as 554 % by selecting the polycarbonate soft segment and the lateral crosslinking. Shape recovery was over 90 % for the entire series and reproducible for four test cycles. The adoption of polycarbonate soft segment and lateral crosslinking significantly could improve the tensile strength and shape recovery compared to PU with polyetherdiol or polyesterdiol soft segment.     

A study on mechanical,thermal and environmental degradation characteristics of N,N-dimethylaniline treated jute fabric-reinforced polypropylene composites

The mechanical and thermal behavior of compression molded jute/polypropylene (PP) composites were studied by evaluating tensile strength (TS), bending strength (BS), tensile modulus (TM), bending modulus (BM), impact strength (IS), thermogravimetric (TG/DTG) and differential thermal analysis (DTA). A chemical modification was made to jute fabrics using N,N-Dimethylaniline (DMA) in order to improve the interfacial adhesion between the fabrics and matrix. It was found that jute fabrics on treatment with N,N-Dimethylaniline (DMA) significantly improved the mechanical properties of the composites. Thermal analytical data of PP, both treated and untreated jute fabrics as well as composites revealed that DMA treatment increased the thermal stability of the fabrics and composite. DMA treatment also reduced the hydrophilic nature of the composite. DMA treated jute composite was found less degradable than control composite under water, soil and simulated weathering conditions.     

Effect of coir fiber content and compatibilizer on the properties of unidirectional coir fiber/polypropylene composites

The main objective of this research was to study the effect of fiber content variation and stearic acid (SA) treatment on the fundamental properties of unidirectional coir fiber (CF) reinforced polypropylene (PP) composites. Several percentages of filler contents were used (10–40 wt %) in order to gain insights into the effect of filler content on the properties of the composites. Coir/PP composites were fabricated by compression molding, and the properties of composites were studied by physico-mechanical and thermal properties. The results from mechanical properties such as tensile strength (TS), tensile modulus (TM) and impact strength (IS) of the CF/PP composites were found to be increased with increasing fiber content, reached an optimum and thereafter decreased with further increase in fiber content. Treatment of the coir with SA as the coupling agent enhanced the mechanical properties, crystallization temperature and crystallinity of virgin PP and water desorption of the resulting composites, resulting from the improved adhesion between the CF and PP matrix. Scanning electron micrographs (SEM) of the tensile fractured samples showed improved adhesion between fiber and matrix upon treatment with SA. Interfacial shear strength (IFSS) of the composites was measured by single fiber fragmentation test (SFFT).     

Enhanced mechanical and thermal properties of carbon fiber composites with polyamide and thermoplastic polyurethane blends

In this article, we demonstrated the preparation of carbon-fiber-reinforced composites using a polyamide 6 (PA6)/thermoplastic polyurethane (TPU) blend, in which the addition of TPU resulted in superior mechanical performances and increased thermal stability. According to various characterization techniques, these results are attributed to an enhanced adhesion and a homogeneous dispersion of long-carbon-fibers (LCFs) with TPU sizing in blended polymer matrix. Above all, dynamic-mechanical thermal analysis (DMTA) measurements clearly show that the dynamic storage modulus (E') of the blend composites is increased by threefold with temperature ranges below and above the glass transition temperature. The presence of LCFs in TPU systems induces effective fiber orientation, exhibiting simultaneous improvements in the tensile strength, flexural strength, and thermal stability.     

EDC/NHS crosslinked electrospun regenerated tussah silk fibroin nanofiber mats

The tussah silk fibroin (TSF) nanofibers with 611 nm diameters were prepared by electrospinning with the solvent hexafluoroisopropanol (HFIP). And then, the TSF nanofibers were crosslinked by 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide/N-Hydroxysuccinimide (EDC/NHS) crosslinking agent. The morphology and microstructure of the crosslinked TSF nanofibers were characterized by scanning electron microscopy (SEM), Fourier transforms infrared analysis (FTIR), X-ray diffraction, Instron electronic strength tester, and cell culture. After treatment with EDC/NHS crosslinking agent, the TSF nanofibers swelled and its average diameter increased from 611 to 841 nm. FTIR and X-ray diffraction results demonstrated that random coil, ??-helix, and ??-sheet co-existed in the TSF nanofiber mats, but the content of ??-sheet increased from 25.26 to 45.34 %, and the random coil content decreased from 32.47 to 24.94 %. Compared with the electrospun pure TSF nanofiber mats, the crosslinked TSF nanofiber mats exhibited a lower breaking tenacity and initial modulus, which were 5.51 MPa and 9.86 MPa, respectively. At the same time, the extension at break of the crosslinked TSF nanofiber achieved 109.38 %. In cell culture evaluation, the crosslinked TSF nanofibers were found to support cell adhesion and spreading fibroblast L373 and bone marrow mesenchymal stem cells (BMSCs), which had potential utility in a range of tissue engineering.     

Effect of mercerization on mechanical, thermal and degradation characteristics of jute fabric-reinforced polypropylene composites

Jute fabric reinforced polypropylene composites were fabricated by compression molding technique. Fiber content in the composites was optimized at 45 % by weight of fiber by evaluating the mechanical parameters such as tensile strength, tensile modulus, bending strength, bending modulus. Surface treatment of jute fabrics was carried out by mercerizing jute fabrics with aqueous solutions of NaOH (5, 10 and 20 %) at different soaking times (30, 60 and 90 mins) and temperatures (0, 30 and 70 °C). The effect of mercerization on weight and dimension of jute fabrics was studied. Mechanical properties of mercerized jute-PP composites were measured and found highest at 20 % NaOH at 0 °C for 60 min soaking time. Thermal analytical data from thermogravimetric and differential thermal analysis showed that mercerized jute-PP composite achieved higher thermal stability compared to PP, jute fabrics and control composite. Degradation characteristics of the composites were studied in soil, water and simulated weathering conditions. Water uptake of the composites was also investigated.     

Preparation and properties of waterborne poly(urethane-urea) ionomers effect of the type of neutralizing agent

A series of waterborne poly(urethane-urea) anionomers were prepared from isophorone diisocyanate (IPDI), polycaprolactone diol (PCL), dimethylol propionic acid (DMPA), ethylene diamine (EDA), and triethylamine (TEA), NaOH, or Cu(COOCH₃)₂ as neutralizing agent. This study was performed to decide the effect of neutralizing agent type on the particle size, viscosity, hydrogen bonding index, adhesive strength, antistaticity, antibacterial and mechanical properties. The particle size of the dispersions decreased in the following order: TEA based samples (T-sample), NaOH based samples(N-sample), and Cu(COOCH₃)₂ based sample (C-sample). The viscosity of the dispersions increased in the order of C-sample, N-sample, and T-sample. Metal salt based film samples (N and C-sample) had much higher antistaticity than TEA based sample. By infrared spectroscopy, it was found that the hydrogen bonding index (or fraction) of samples decreased in the order of T-sample, N-sample, and C-sample. The adhesive strength and tensile modulus/strength decreased in the order of T-sample, N-sample, and C-sample. The C-sample had strong antibacterial halo, however, T- and N-samples did not.     

Hybrid multi-scale basalt fiber-epoxy composite laminate reinforced with Electrospun polyurethane nanofibers containing carbon nanotubes

In this study, we report the fabrication and evaluation of a hybrid multi-scale basalt fiber/epoxy composite laminate reinforced with layers of electrospun carbon nanotube/polyurethane (CNT/PU) nanofibers. Electrospun polyurethane mats containing 1, 3 and 5 wt% carbon nanotubes (CNTs) were interleaved between layers of basalt fibers laminated with epoxy through vacuum-assisted resin transfer molding (VARTM) process. The strength and stiffness of composites for each configuration were tested by tensile and flexural tests, and SEM analysis was conducted to observe the morphology of the composites. The results showed increase in tensile strength (4–13 %) and tensile modulus (6–20 %), and also increase in flexural strength (6.5–17.3 %) and stiffness of the hybrid composites with the increase of CNT content in PU nanofibers. The use of surfactant to disperse CNTs in the electrospun PU reinforcement resulted to the highest increase in both tensile and flexural properties, which is attributed to the homogeneous dispersion of CNTs in the PU nanofibers and the high surface area of the nanofibers themselves. Here, the use of multi-scale reinforcement fillers with good and homogeneous dispersion for epoxy-based laminates showed increased mechanical performance of the hybrid composite laminates.     

The grafting of recycled polyol from waste polyurethane foam onto new polyurethane and its impact on shape recovery and water vapor permeation

Recycled polyols from waste polyurethane (PU) foams were grafted onto PU to improve the properties such as tensile strength, shape recovery, low-temperature flexibility, and water compatibility. The recycled polyol was either purified by column chromatography before grafting or was used directly for grafting. The soft segment melting temperature of PU did not notably increase with the addition of polyol, whereas the glass transition temperature increased with increased polyol content. The tensile strength sharply increased at low polyol content and decreased at high polyol content, while the strain at break did not significantly change with an increase in polyol content. The shape recovery at 10 oC notably improved compared with unmodified PU and remained high after four cyclic tests. Polyol-grafted PU demonstrated better lowtemperature flexibility and reduced the water vapor permeability of PU membranes. Overall, grafting recycled polyol onto PU significantly improved the tensile stress, shape recovery, and low-temperature flexibility of PU.     

Structural,thermal, and mechanical properties of polyurethane foams prepared with starch as the main component of polyols

In this study, rigid polyurethane foams were prepared using starch as the main component of polyols and their structural, thermal, and mechanical properties were investigated. The starch content in polyols was 30∼50 wt.%. The prepared polyurethane foams had a cell structure. When the starch content and -NCO/-OH molar ratio (TS4-05, TS3-07, and TS3-05) was low, polyurethane foams were not formed. To confirm the formation of a urethane linkage between -OH of the starch and -NCO of the 2,4-TDI, FT-IR spectroscopic analysis was performed. The thermal properties of polyurethane foams were analyzed by DSC and TGA. DSC thermograms showed two endothermic peaks: a sharp peak at a lower temperature and a broad peak at a higher temperature. Both peaks were shifted to higher temperature with starch content in polyols and -NCO/-OH molar ratio. Thermal degradation of polyurethane foams began at a lower temperature and ended at a higher temperature than that of starch. The impact resistance, compressive stress and modulus of polyurethane foams increased with -NCO/-OH molar ratio and starch content.     

Wear minimization of ultra high molecular weight polyethylene by benzophenone-assisted photocrosslinking

Ultra high molecular weight polyethylene (UHMWPE) containing benzophenone (BP) is photocrosslinked under continuous UV irradiation. BP addition as low as 0.77 mol% per repeating unit of UHMWPE is enough to increase the gel fraction up to 99.8 %. The crosslinks are formed through the recombination of methine radicals generated from the hydrogen abstraction of UHMWPE by the excited BP. The heat of fusion of UHMWPE reduces substantially and the peak decomposition temperature increases as much as 15.8 oC due to the crosslinked network, coupled with slight decrease in crystallinity. The tensile strength, modulus and toughness of the crosslinked UHMWPE film are significantly improved with increasing crosslinking density. The wear rate of the UHMWPE also remarkably decreases from 10.2 mg/million cycles to 1.9 mg/million cycles, which can minimize the wear of total hip joint anthroplasty bearings.     

Preparation and characterization of PVA/PU blend nanofiber mats by dual-jet electrospinning

A series of blend nanofiber mats comprising poly(vinyl alcohol) (PVA) and polyurethane (PU) were prepared by dual-jet electrospinning in various parameters. Orthogonal experimental design was used to investigate how those parameters affected on fiber diameters and fiber diameter distribution. Altogether three parameters having three levels each were chosen for this study. The chosen parameters were tip-to-collector distance (TCD), voltage and tip-to-tip distance (TTD). Fiber diameters, thermal properties, mechanical properties and hydrophilicity of the blend nanofiber mats were examined by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), tensile test, contact angle and water absorption test, respectively. The results showed that the optimum conditions for PVA/PU blend nanofiber mats fabricated by dual-jet electrospinning were TCD of 20 cm, voltage of 18 kV and TTD of 4 cm. Besides, the thermal stability of PVA/PU blend nanofiber mats had been improved compared with pure nanofibers. Furthermore, the elongation and tensile strength of the blend nanofiber mats were significantly increased compared with pure PVA and pure PU, respectively. And the blend nanofiber mats exhibited well hydrophilicity.     

Electrospun curcumin loaded poly(lactic acid) nanofiber mat on the flexible crosslinked PVA/PEG membrane film: Characterization and <Emphasis Type="Italic">in vitro</Emphasis> release kinetic study

Herein, a biodegradable and biocompatible composite comprising of support membrane based on crosslinked PVA/PEG film and curcumin loaded electrospun poly(lactic acid) (PLA) nanofiber mat is introduced. The membrane film was prepared from PVA/PEG blend followed by crosslinking with an optimum amount of citric acid, 15 wt.%. After then, PLA solutions with different curcumin content, 0-11 wt.%, were electrospinned on the prepared membrane substrate. The prepared film showed high water absorption, water vapor transmission rate and superior mechanical properties with improved elastic modulus, tensile strength and with an elongation of around 320 % with respect to the non-crosslinked one. Also, the scanning electron microscopy was revealed uniformly dispersed pores throughout the membrane film with a nearly narrow in size distribution centered at 36 μm. As well, a nanostructure porous morphology was found for the electrospun fibrous curcumin loaded PLA from the scanning electron microscopy micrographs and the average fiber diameter was decreased with curcumin content. In vitro drug release from the prepared flexible composite into the vertical diffusion cell was recorded by the measuring curcuminoids content using high performance liquid chromatography and drug release kinetic evaluations were revealed that the release pattern of all prepared samples, containing different content of curcumin, well fitted to the Higuchi’s model signifying diffusion-controlled release mechanism. As well, the determined release rate at the second release stages, i.e. steady state flux (J), was varied from 0.31 to 43.53 μg·cm^-2·h^-1 with increasing drug content from 1 to 11 wt.%. Regarding this results, this flexible composite by providing the moist environment along with miraculous healing properties of curcumin, can be potential candidate for transdermal drug delivery.     

优质绿茶加工过程主要物理特性变化的研究

以茶树单芽和一芽一叶为试验材料,采用恒重法、量筒法、TPA测试和应力应变拉伸测试,研究针形名优绿茶加工过程物料容重、质构特性和拉伸等物理特性的变化规律。结果表明,在针形绿茶加工过程中,茶叶容重呈先增后减的趋势,峰值出现在揉捻叶（含水量56%~58%）,做形后期、固形和干燥过程茶叶容重急剧下降。塑性也呈现先增后降的趋势,在揉捻工序达到最大值,其后在做形过程（含水量58%~23%）均维持在较高水平,而在固形和干燥阶段显著下降。弹性的变化趋势与塑性相反,呈先下降再升高的趋势,在揉捻及做形过程（含水量58%~23%）处于最低水平。加工过程柔软性的变化幅度较小。茶叶的拉伸过程经历线性阶段、非线性阶段和塑性变形到断裂阶段。随着加工的进程,最大力呈先下降后升高（含水率56%~57%）的趋势,拉伸强度则呈增加趋势,弹性模量在揉捻前变化小（含水率56%~57%）,但此后显著增加。相关性分析表明,加工过程茶叶的拉伸强度与含水率呈极显著的负相关。研究结果还表明,单芽和一芽一叶的主要物理特性在加工过程的变化不尽相同。除柔软性接近外,单芽原料的容重、弹性、最大力要高于一芽一叶,但塑性、拉伸强度、弹性模量要小于一芽一叶。除了塑性和柔软性接近外,单芽在各工序的容重和弹性均高于一芽一叶,但一芽一叶的弹性模量和拉伸强度在全过程均高于单芽,最大力在揉捻后显著高于单芽。说明在机械设计原理和加工工艺的掌握方面需要注意原料的差异性。     

A new catalyst for glyoxal durable press finish of cotton fabrics

Aluminum ammonium sulfate was used as a new catalyst for glyoxal to minimize the decrease of physical properties of durable press cotton fabrics, and the optimum treatment conditions such as the concentration of glyoxal, molar ratio of catalyst to glyoxal, curing temperature and time were investigated. The retention of tensile strength and the whiteness of fabrics treated with glyoxal/aluminum ammonium sulfate was increased as much as to the degree of that obtained with glyoxal/aluminum sulfate while wrinkle recovery angles were as good as those of the latter. Some additives such as DEG, polyurethane and softener were used to improve the physical properties. When DEG or polyurethane was added to the glyoxal padding solution, wrinkle recovery angle (WRA) significantly increased while tensile strength and whiteness were not influenced. DEG added to the glyoxal padding solution increased the durability of DP finish. The softener added to the glyoxal padding solution increased the WRA of treated fabrics while it decreased the tensile strength slightly. The whiteness of fabrics treated with glyoxal alone increased while the WRA decreased slightly.     

Elastic property of polyolefin elastomer film cross linked by electron beam irradiation

Polyolefin elastomers were extruded to form films and subjected to electron beam (EB) irradiation at various energy levels. The film samples were characterized to illuminate the effects of EB-induced cross-linking through measurements of gel contents, Fourier transform infra-red (FT-IR) spectroscopy, and variations of tensile properties of the films after the EB irradiations. The EB irradiations introduced crosslinking among the molecular chains resulting increases in initial modulus. The elastic recovery was 83 % at 30 % stain, which is increased by 10 % at 150 kGy compared with pristine. The maximum stain was 1,400 % at 150 kGy which is comparable with commercial polyurethane elastomer.