Recent Advances in Environment-Friendly Polyurethanes from Polyols Recovered from the Recycling and Renewable Resources: A Review.

Polyurethane (PU) is among the most universal polymers and has been extensively applied in many fields, such as construction, machinery, furniture, clothing, textile, packaging and biomedicine. Traditionally, as the main starting materials for PU, polyols deeply depend on petroleum stock. From the perspective of recycling and environmental friendliness, advanced PU synthesis, using diversified resources as feedstocks, aims to develop versatile products with excellent properties to achieve the transformation from a fossil fuel-driven energy economy to renewable and sustainable ones. This review focuses on the recent development in the synthesis and modification of PU by extracting value-added monomers for polyols from waste polymers and natural bio-based polymers, such as the recycled waste polymers: polyethylene terephthalate (PET), PU and polycarbonate (PC); the biomaterials: vegetable oil, lignin, cashew nut shell liquid and plant straw; and biomacromolecules: polysaccharides and protein. To design these advanced polyurethane formulations, it is essential to understand the structure-property relationships of PU from recycling polyols. In a word, this bottom-up path provides a material recycling approach to PU design for printing and packaging, as well as biomedical, building and wearable electronics applications.

Effect of Different Silane Coupling Agents on Properties of Waste Corrugated Paper Fiber/Polylactic Acid Composites.

The surface of plant fibers was modified by silane coupling agents to prepare plant fiber/polylactic acid (PLA) composites, which can improve the dispersion, adhesion, and compatibility between the plant fibers and the PLA matrix. In this work, three silane coupling agents (KH550, KH560, and KH570) with different molecular structures were used to modify the surface of waste corrugated paper fibers (WFs), and dichloromethane was used as the solvent to prepare the WF/PLA composites. The effects of different silane coupling agents on the microstructure, mechanical properties, thermal decomposition, and crystallization properties of the composites were studied. The mechanical properties of the composites treated with 4 wt% KH560 were the best. Silane coupling agents can slightly improve the melting temperature of the composites, and WFs can promote the crystallization of PLA. The modification of WFs by silane coupling agents can increase the decomposition temperature of the WF/PLA composites. The content and type of silane coupling agent directly affected the mechanical properties of the WF/PLA composites. The interfacial compatibility between the WFs and PLA can be improved by using a silane coupling agent, which can further enhance the mechanical properties of WF/PLA composites. This provides a research basis for the further improvement of the performance of plant fiber/PLA composites.

Synthesis and Properties of Carbon Microspheres from Waste Office Paper.

As a kind of biomass resource, waste office paper can be used as a carbon precursor to prepare carbon materials. In this work, carbon microspheres with regular shape, uniform particle size and high carbon content were successfully prepared from waste office paper via a hydrothermal synthesis method with sulfuric acid as the catalyst. The effects of reaction temperature and sulfuric acid dosage on the morphology of the carbon microspheres were studied. The formation mechanism of the carbon microspheres was investigated by analyzing the structure and composition of the products. The results show that the hydrolysis of cellulose in waste paper under hydrothermal conditions was the key for the formation of carbon microspheres. The temperature of hydrothermal reaction and the use of sulfuric acid can affect the morphology of carbon microspheres. The carbon microspheres synthesized at 210 °C with 10 mL sulfuric acid have the best surface morphology, with uniform particle size and higher dispersion. Cyclic voltammetry and electrochemical impedance spectroscopy show that the carbon microspheres have good capacitance performance and can be used in capacitors. This study provides a low-cost precursor for carbon microspheres as well as a new method for the recycle of waste paper.

The Mechanical Behavior and Enhancement Mechanism of Short Carbon Fiber Reinforced AFS Interface.

The aluminum foam sandwich (AFS), which perfectly combines the excellent merits of an aluminum foam core and face sheet materials, has extensive and reliable applications in many fields, such as aerospace, military equipment, transportation, and so on. Adhesive bonding is one of the most widely used methods to produce AFS due to its general applicability, simple process, and low cost, however, the bonding interface is known as the weak link and may cause a serious accident. To overcome the shortcomings of a bonded AFS interface, short carbon fiber as a reinforcement phase was introduced to epoxy resin to reinforce the interface adhesion strength of AFS. Single lap shear tests and three-point bending tests were conducted to study the mechanical behavior of the reinforced interface and AFS, respectively. The failure mechanism was studied through a macro- and microanalysis. The result showed that after the reinforcement of carbon fiber, the tangential shear strength of the interface increased by 73.65%. The effective displacement of AFS prepared by the reinforced epoxy resin is 125.95% more than the AFS prepared by the unreinforced epoxy resin. The flexure behavior of the reinforced AFS can be compared with AFS made through a metallurgical method. Three categories of reinforcement mechanisms were discovered: (a) the pull off and pull mechanism: when the modified carbon fiber performed as the bridge, the bonding strength improved because of the pull off and pull out of fibers; (b) adhesion effect: the carbon fiber gathered in the hole edge resulted in epoxy resins being gathered in there too, which increased the effective bonding area of the interface; (c) mechanical self-locking effect: the carbon fiber enhanced the adhesive filling performance of aluminum foam holes, which improved the mechanical self-locking effect of the bonding interface.

Facile preparation and characterization of fibrous carbon nanomaterial from waste polyethylene terephthalate.

Efficient reduction of environmental pollution caused by waste polyethylene terephthalate (PET) and production of carbon nanomaterials are desirable for nanotechnology, printable electronics, composites and environment protection. Here we report a simple top-down micro/nano-fabrication process to prepare fibrous carbon nanomaterial from waste PET bottles. This process is highly efficient, facile, and catalyst-free in preparing fibrous carbon nanomaterial with promising hydrophobic and electrical properties. The fibrous carbon nanomaterial can be used both in the form of sheet or powder, and it supplies a versatile surface for preparing novel carbon-based composites with significant optical properties and conductivity. The prepared carbon nanomaterial from waste PET has also been used in fabricating strain sensor with good durability.

Author Correction: Various nanoparticle morphologies and surface properties of waterborne polyurethane controlled by water.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

New approach to recycle office waste paper: Reinforcement for polyurethane with nano cellulose crystals extracted from waste paper.

New approach to recycle office waste paper was purposed in this paper, i.e., cellulose nanocrystal (CNC) was extracted from waste paper and then used CNC as the organic filler to reinforce polyurethane elastomer (PUE) in thermal properties. A series of CNC/PUE nanocomposites was prepared in situ using a two-step process in solvent N,N-dimethylformamide solution by changing the content of CNC from 0.5, 1, 2, 3, 4 to 5 wt%. The results showed that CNC was covalently bonded to PUE, and specifically concerned with the hard segments of PUE resulting from the strong hydrogen bonding. The interactions between CNC and PUE caused the increased thermal and thermo-mechanical properties, and decreased water absorption of nanocomposites. Importantly, the initial degradation temperature of PUE with 2 wt% content CNC (CNC/PUE2) increased by 21 °C. CNC/PUE2 had the better comprehensive properties with the worse water absorption, which made CNC/PUE2 appealing in load bearing and outdoor applications. Hence, this work not only provided a new recycling method of waste paper but also provided a thermolstable PUE with lower cost.

Structure and thermal properties of various alcoholysis products from waste poly(ethylene terephthalate).

Waste polyethylene terephthalate (PET) has been a core member in plastic polluters due to the great amount consumption in food packaging, soft-drink bottles, fibers and films. It is essential to recycle waste PET and alcoholysis is a significant way to accomplish chemical recycling. In this work, three kinds of dihydric alcohols, including neopentyl glycol (NPG), dipropylene glycol (DPG) and poly(propylene glycol) (PPG), were employed to decompose waste PET with different temperatures, catalysts, and PET. A series of alcoholysis products with different appearance were obtained. The bulk structure and thermal properties of alcoholysis products were investigated by FTIR, 1H NMR, MALDI-TOF, DSC and TG experiments. It is found that poly(propylene glycol) may react with waste PET to generate copolymer instead of oligomer products, dimers or trimers, etc. This product possesses excellent shelf stability and present transparent appearance, which may hold a great potential application in chemical industry. Moreover, the alcoholysis activity of DPG is the lowest comparing with NPG and EG in degradation of waste PET.

Eco-friendly waterborne polyurethane reinforced with cellulose nanocrystal from office waste paper by two different methods.

Focusing on eco-friendly materials, cellulose nanocrystal (CNC) extracted from office waste paper was used to reinforce waterborne polyurethane (WPU) with varying content by two incorporation routes including blending method by sonication after WPU synthesis (BCNC/WPU) and the alternative in-situ during the WPU synthesis process (CNC/WPU). The results showed that new interaction between CNC and WPU through hydrogen bonds in the interfacial area was formed and CNC reinforced hard segments effectively. However, the interaction in BCNC/WPU was not as stronger as that in CNC/WPU. Besides, CNC improved thermal stability of WPU remarkably, especially BCNC/WPU. The addition of CNC caused a delay around 50 °C in the start of the degradation process, and a delay of 5-18 °C and 2-20 °C in the temperatures at 10 and 50 wt% weight loss, respectively. These eco-friendly and biodegradable novel materials have potential applications in medical and biologic fields.

Facile Preparation of Hydrophobic Aluminum Oxide Film via Sol-Gel Method.

Hydrophobic aluminum oxide films (AOFs) are widely used in anti-oxidation and anti-corrosion applications. In preparing AOFs, complex and high temperature conditions are usually necessary. Here, we report aluminum nanowire structures with hydrophobic properties, prepared using a facile sol-gel method by magnetic stirrer and hydrothermal reaction. The electromagnetic force work has great influence on the structure of AOFs. The surface morphology and compositions of the AOFs were analyzed by scanning electron microscope (SEM), energy dispersive X-ray spec-trometers (EDS), X-ray diffraction (XRD), 3M peeling test, and X-ray photoelectron spectroscopy (XPS). With the increase of water content in hydrothermal reaction, the hydrophobicity of AOFs proportional increased. Adding 10 ml deionized water leads to the formation of the upper nanowires and the lower nanohole with 129.3° water contact angle. Meanwhile, the AOF provide a good substrate for electroless deposition (ELD) of copper (Cu) to achieve a simple fabrication of metal conductor.

Polyurethane elastomer composites reinforced with waste natural cellulosic fibers from office paper in thermal properties.

Polyurethane elastomer (PUE) composites were synthesized with a low additive content of waste natural cellulosic fibers from office paper. A new technology combining prepolymer method with physical blending and modification was adopted. The results showed that cellulosic fibers were covalently bonded to polyurethane molecular chains and served as a cross-linking agent making the degree of phase separation decrease. Even so, the lowest additive content of cellulosic fibers (1 wt%) in this work could make polyurethane still hold a certain degree of phase separation. Besides, thermal stability of polyurethane was improved from 288 to around 300 °C even at the low cellulosic fibers content. PUE with 3% cellulosic fibers had the better interfacial compatibility between cellulosic fibers and polyurethane causing the greater thermal reinforcement. PUE with 4% and 5% cellulosic fibers had the worse interfacial compatibility generating the better damping capacity indicating that cellulosic fibers could improve damping performance of polyurethane, especially polyurethane with 5 wt% fibers. It meant that cellulosic fibers had a potential application in damping materials.

Effect of multi-walled carbon nanotubes on the physical properties and crystallisation of recycled PET/TPU composites.

Thermoplastic polyurethane (TPU) was blended with recycled polyethylene terephthalate (rPET) to prepare rPET/thermoplastic polyurethane (TPU) composites. Meanwhile, multiple-walled carbon nanotubes (MWCNTs) were employed as a reinforcing filler to study the synergistic effect between CNTs and rPET/TPU composites. The effect of CNT content on the morphology and micro-structure of the composites was investigated using a scanning electron microscope (SEM) and X-ray diffraction (XRD). The thermal properties were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The mechanical properties were investigated using tensile tests and hardness measurements. The results showed that TPU was compatible with rPET. The existence of rPET changed the crystalline phase and affected the glass transition and crystallisation temperature of the TPU matrix. The rPET/TPU composites displayed poor thermal stability and tensile properties when compared to pure TPU. The addition of CNTs had no effect on the crystalline phase of the rPET/TPU composites. Due to the occurrence of interfacial adhesion between the CNTs and rPET, the CNTs displayed an offset effect on the reaction of rPET and decreased the rigidity of the molecular chain in the rPET/TPU composites. The thermal stability and tensile strength of the CNTs/rPET/TPU composites improved with an increase in CNT content.

Cellulose nanocrystals obtained from office waste paper and their potential application in PET packing materials.

Annually a tremendous amount of office waste paper (OWP) is discarded creating environmental pollution. Therefore, how to make this paper from waste to wealth and use it in new approaches have become a meaningful and challenging work. In this work, OWP being a cellulose rich biomass was employed for the production of cellulose nanocrystals (CNCs) by acid hydrolysis with different acid concentrations but without subjecting OWP to alkali and bleaching treatments. The testing results showed that CNCs prepared using sulfuric acid concentration of 59% with respect to OWP had the highest crystallinity and this concentration was the transition concentration for the production of opaque CNCs film with convoluted nanofibers to transparent one with orientated nanofibers. Besides, CNCs prepared using acid concentration of 65% coated on PET sheet not only had a better water vapor barrier property but also was on a par with the transparency of PET, which was hopeful to be used as coating materials in packaging materials.

Various nanoparticle morphologies and surface properties of waterborne polyurethane controlled by water.

Water plays important roles in organic reactions such as polyurethane synthesis, and the aqueous solution environment affects polymer morphology and other properties. This paper focuses on the morphology and surface properties of waterborne polyurethane resulting from the organic reaction in water involving different forms (solid and liquid), temperatures and aqueous solutions. We provide evidence from TEM observations that the appearance of polyurethane nanoparticles in aqueous solutions presents diverse forms, including imperfect spheres, perfect spheres, perfect and homogenous spheres and tubes. Based on the results on FTIR, GPC, AFM and XRD experiments, we suggest that the shape of the nanoparticles may be decided by the crimp degree (i.e., the degree of polyurethane chains intertangling in the water environment) and order degree, which are determined by the molecular weight (Mn) and hydrogen bonds. Meanwhile, solid water and high-temperature water can both reduce hard segments that gather on the polyurethane film surface to reduce hydrophilic groups and produce a soft surface. Our findings show that water may play key roles in aqueous polymer formation and bring order to molecular chains.