Ambient air-operated thermo-switchable adhesion of N-isopropylacrylamide-incorporated pressure sensitive adhesives.

Owing to the rise in global population and living standards, waste treatment has inevitably become a critical issue for a sustainable environment. In particular, for an effective recycling process, it is vital to disassemble different types of materials by removing adhesives used in the packaging. However, this removal process requires harsh solvents (acidic and organic) that are unfriendly to nature and may cause additional pollution. To address this issue, functional adhesive materials that can be removed without the use of harsh solvents have drawn significant attention. One promising approach is to utilize the stimuli-responsive polymers to synthesize pressure sensitive adhesives (PSAs); however, it is technically challenging to simultaneously satisfy (i) strong initial adhesion (without stimulus), (ii) stimuli-responsive sufficient reduction of adhesion, and (iii) reversibility. In this study, thermo-switchable PSAs were synthesized by copolymerizing N-isopropylacrylamide (NIPAM), which possesses thermal-responsive properties; acrylic acid, which endows adhesive properties; and 2-ethylhexyl acrylate, which has a low glass transition temperature to attain sufficient flexibility. The synthesized NIPAM-based thermo-switchable PSAs exhibited significantly high peel strength at room temperature (∼15.41 N/25 mm at 20 °C), which decreased by ∼97% upon heating (∼0.46 N/25 mm at 80 °C). Importantly, no residues remained due to the cohesive nature of NIPAM at high temperature. The reversible adhesion behaviour of the thermo-switchable PSAs was retained during repeated heating and cooling cycles. Therefore, the developed thermo-switchable PSA can enhance the reusability and recyclability of valuable materials and minimize the use of toxic chemicals for adhesive removal, contributing to a more sustainable future.

Development of Poly(methyl methacrylate)-Based Copolymers with Improved Heat Resistance and Reduced Moisture Absorption.

Poly(methyl methacrylate) (PMMA) is widely used as a transparent material for optical applications, owing to its high light transmittance. However, it exhibits poor heat resistance and high moisture absorption, leading to distortion and deformation upon exposure to elevated temperatures and/or moisture. These structural changes decrease the transparency of PMMA, critically limiting its applicability. In this study, we synthesized poly(methyl methacrylate-co-styrene-co-acrylamide) (PMSAm) as a reference polymer and introduced one of four different comonomers [N-phenylmaleimide (PMI), N-cyclohexylmaleimide (CHMI), allyltrimethylsilane (ATMS), or 2,2,2-trifluoroethyl methacrylate (TF)] as a means to improve heat resistance and reduce moisture absorption. Four series of PMMA-based random copolymers (PMSAm-PMI, PMSAm-CHMI, PMSAm-ATMS, and PMSAm-TF) were synthesized by conventional thermal radical polymerization. All of the polymers synthesized exhibited improved heat resistance, with PMSAm-CHMI exhibiting the highest glass transition temperature (Tg = 122.54 °C) and 5% weight loss thermal decomposition temperature (T5d = 343.40 °C) as well as the lowest thermal expansion coefficient (90.3 µm m-1 °C-1). The highest hydrophobicity was exhibited by PMSAm-TF, with a water contact angle of 78.9°, indicating higher hydrophobicity compared to that of pure PMMA (69.4°). More importantly, high transparency (∼90%) was exhibited by all of the synthesized polymers. Thus, our copolymerization strategy successfully addresses the limitations, i.e., low heat resistance and high moisture absorption, of conventional PMMA-based materials.

Co-functionalized organic/inorganic hybrid ZnO nanorods as electron transporting layers for inverted organic solar cells.

In an unprecedented attempt, we present an interesting approach of coupling solution processed ZnO planar nanorods (NRs) by an organic small molecule (SM) with a strong electron withdrawing cyano moiety and the carboxylic group as binding sites by a facile co-functionalization approach. Direct functionalization by SMs (SM-ZnO NRs) leads to higher aggregation owing to the weaker solubility of SMs in solutions of ZnO NRs dispersed in chlorobenzene (CB). A prior addition of organic 2-(2-methoxyethoxy)acetic acid (MEA) over ZnO NRs not only inhibits aggregation of SMs over ZnO NRs, but also provides enough sites for the SM to strongly couple with the ZnO NRs to yield transparent SM-MEA-ZnO NRs hybrids that exhibited excellent capability as electron transporting layers (ETLs) in inverted organic solar cells (iOSCs) of P3HT:PC60BM bulk-heterojunction (BHJ) photoactive layers. A strongly coupled SM-MEA-ZnO NR hybrid reduces the series resistance by enhancing the interfacial area and tunes the energy level alignment at the interface between the (indium-doped tin oxide, ITO) cathode and BHJ photoactive layers. A significant enhancement in power conversion efficiency (PCE) was achieved for iOSCs comprising ETLs of SM-MEA-ZnO NRs (3.64%) advancing from 0.9% for pristine ZnO NRs, while the iOSCs of aggregated SM-ZnO NRs ETL exhibited a much lower PCE of 2.6%, thus demonstrating the potential of the co-functionalization approach. The superiority of the co-functionalized SM-MEA-ZnO NRs ETL is also evident from the highest PCE of 7.38% obtained for the iOSCs comprising BHJ of PTB7-Th:PC60BM compared with extremely poor 0.05% for non-functionalized ZnO NRs.

Roles of interfacial modifiers in hybrid solar cells: inorganic/polymer bilayer vs inorganic/polymer:fullerene bulk heterojunction.

Hybrid solar cells (HSCs) incorporating both organic and inorganic materials typically have significant interfacial issues which can significantly limit the device efficiency by allowing charge recombination, macroscopic phase separation, and nonideal contact. All these issues can be mitigated by applying carefully designed interfacial modifiers (IMs). In an attempt to further understand the function of these IMs, we investigated two IMs in two different HSCs structures: an inverted bilayer HSC of ZnO:poly(3-hexylthiophene) (P3HT) and an inverted bulk heterojunction (BHJ) solar cell of ZnO/P3HT:[6,6]-phenyl C61-butyric acid methyl ester (PCBM). In the former device configuration, ZnO serves as the n-type semiconductor, while in the latter device configuration, it functions as an electron transport layer (ETL)/hole blocking layer (HBL). In the ZnO:P3HT bilayer device, after the interfacial modification, a power conversion efficiency (PCE) of 0.42% with improved Voc and FF and a significantly increased Jsc was obtained. In the ZnO/P3HT:PCBM based BHJ device, including IMs also improved the PCE to 4.69% with an increase in Voc and FF. Our work clearly demonstrates that IMs help to reduce both the charge recombination and leakage current by minimizing the number of defect sites and traps and to increase the compatibility of hydrophilic ZnO with the organic layers. Furthermore, the major role of IMs depends on the function of ZnO in different device configurations, either as n-type semiconductor in bilayer devices or as ETL/HBL in BHJ devices. We conclude by offering insights for designing ideal IMs in future efforts, in order to achieve high-efficiency in both ZnO:polymer bilayer structure and ZnO/polymer:PCBM BHJ devices.