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Poly-N-vinyl carbazole-iodine charge transfer photovoltaic effect spectral and intensity dependence, noting possible radiation detection and energy conversion applications
It is well known that the rate of plasma polymerization, or deposition rate, of a given monomer depends on various plasma process parameters, e.g., monomer flow rate, pressure, power, frequency (DC, rf or microwave), location of the substrate in the reactor, reactor geometry or configuration, and temperature. In contrast, little work has been done to relate deposition rates to monomer structures for a homologous series of monomers where the rates are obtained under identical plasma process parameters. For the particular series of fluorinated ethylenes (C2HxF4-x; x = 0-4), deposition rates were reported for ethylene (ET), vinyl fluoride, vinylidene fluoride and tetrafluoroethylene (TFE), but for plasma polymerizations carried out under different discharge conditions, e.g., pressure, current density, and electrode temperature. Apparently, relative deposition rates were reported for only two members of that series (ET, x = 4, and TFE, x = 0) for which the plasma polymerizations were conducted under identical conditions. We now present relative deposition rates for both homopolymerizations and copolymerizations of the entire series of fluorinated ethylenes (x = 0-4). Our interest in such rates stems from prior work on the plasma copolymerization of ET and TFE in which it was found that the deposition rates for the plasma copolymers, when plotted versus mol % TFE in the ET/TFE feed stock, followed a concave-downward curve situated above the straight line joining the deposition rates for the plasma homopolymers. This type of plot (observed also for an argon-ET/TFE plasma copolymerization) indicated a positive interaction between ET and TFE such that each monomer apparently "sensitized" the plasma copolymerization of the other. Since the shape of that plot is not altered if mol % TFE is replaced by F/C, the fluorine-to-carbon ratio, this paper aims (1) to show how the relative deposition rates for plasma copolymers drawn from all pairs of monomers in the C2HxF4-x series, as well as the deposition rates for the individual plasma homopolymers, vary with F/C ratios of the monomers or monomer blends, and (2) to see if those rates give rise to a common plot.
This Annual Performance Monitoring Report (PMR) for the Dense Non-Aqueous Phase Liquid (DNAPL) Source Zone (DSZ) and Hot Spot 6 (HS 6) Air Sparge (AS) System presents the results of Year 12 operation of the hydraulic containment (HC) Interim Measure (IM), the results of performance monitoring direct-push technology (DPT) sampling and monitoring well sampling conducted in the DSZ, and the results of operations and performance sampling of the HS 6 AS IM at Launch Complex 34 (LC34), located at Cape Canaveral Space Force Station (CCSFS), Florida. Site-wide biennial LTM sampling was not conducted during this reporting period and is scheduled to be conducted in December 2022. The timeframe for activities documented in this PMR extends from April 1, 2021 to March 31, 2022. LC34 has been designated Solid Waste Management Unit CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act Corrective Action Program. The objective of the HC IM at LC34 is to contain the DSZ and deep dissolved-phase trichloroethene (TCE) high concentration plume via operation of a hydraulic containment system (HCS). The pre-IM design 300 micrograms per liter (μg/L) TCE groundwater contour was used to establish the deep zone capture area for deep recovery wells, and the shallow zone capture area was defined by the DSZ. The system began operating in 2010, and in 2015, the system was expanded to provide HC for areas within the 300 μg/L TCE groundwater isocontours of HS 3 and 4. In 2018 and 2019, an investigation was conducted to re-characterize the DSZ, which included investigating TCE mass in Layer 7. This data was subsequently used to optimize the pumping rates of the HCS to more adequately capture residual contaminant mass. The operational period for Year 12 of the HCS was from April 1, 2021 to March 31, 2022. Operational runtime for the system was 94 percent during Year 12, with downtime events attributed to planned maintenance, system repairs, and power outages. As of March 31, 2022, a total of 285,712,801 gallons of groundwater containing 84,933 pounds of VOCs have been removed by the HCS. Influent concentrations of TCE have decreased since startup from approximately 280,000 µg/L (January 2010) to 12,000 µg/L (March 2022). During the reporting period, all effluent concentrations from the HCS (aqueous and vapor) were below regulatory reporting limits, indicating the system continues to operate as intended. Performance monitoring was conducted in December 2021 within the DSZ to evaluate TCE contamination. Groundwater samples were collected via DPT at nine locations, consistent with previous events in 2017, 2018, 2019, and 2020. Full vertical profile sampling was completed at each DPT from 8 to 98 ft bls, at 5 foot intervals. The DPT performance monitoring results are summarized in this PMR. The results revealed TCE remains at concentrations greater than 11,000 µg/L in the DSZ (1-percent solubility, indicative of DNAPL) at eight of the nine DPT locations at depths ranging from 8 to 98 ft bls. An overall increasing trend of TCE concentrations was observed in DPT samples during this reporting period, which may be due to several recovery wells that were turned off during the AS Pilot Study in the DSZ that operated from July 2021 to February 2022 (documented separately from this report). The maximum TCE concentration in 2021 was 15,400,000 µg/L in the 58 ft bls depth interval at DPT597 (previous maximum result in 2020 was 1,690,000 at 48 ft bls at DPT596). During the 2021 DPT event, the overall majority of TCE contamination was identified in the 58 ft bls interval (below Layer 4), where in the previous year the majority of mass was observed in Layer 4. This trend appears to indicate continued mass discharge from Layer 4 (fine-grained unit). In addition to DPT sampling, monitoring well samples were collected from deep wells in the DSZ area (Layers 7 and 8) to verify vertical delineation. All monitoring well results were non-detect or below cleanup levels, with exception of one well (IW0162, screened 105 to 115 ft bls, which is below the existing recovery well capture zone) where TCE was identified above cleanup target levels. The HS 6 AS system remained operational during the reporting period covered under this report. The HS 6 AS IM was initiated in 2018 with 160 AS wells, and expanded in 2019 with an additional 140 AS wells. Quarterly performance monitoring was reduced to semi-annual prior to this operational period. The results of the HS 6 system operation and semi-annual performance monitoring are summarized in this report. Semi-annual monitoring results collected in April and October 2021 show concentrations of contaminants of concern (cis-1,2-dichloroethene, trans-1,2- dichloroethene, and vinyl chloride) are generally decreasing and not impacting the surface water drainage canal, indicating the HS 6 IM is meeting objectives. Overall, the tasks associated with Year 12 operation of the HC IM and operation of the HS 6 AS IM were performed in accordance with the recommendations of the 2020 LC34 (Year 11) Operations, Maintenance, and Monitoring Report for DNAPL Source Zone, Site Wide LongTerm Monitoring, and Hot Spot 6 Air Sparging System PMR (NASA, 2021c). Evaluation of results from the HC IM and HS 6 IM show that these systems are operating as designed and meeting performance objectives.
This Air Sparge (AS) System Construction Completion, Performance Monitoring, and Long-Term Monitoring (LTM) Report presents activities conducted at the Paint and Oil Locker (POL) (Solid Waste Management Unit [SWMU] 067) and Supply Warehouse #3 (SW3) (SWMU 088) sites located at the Kennedy Space Center (KSC), Florida. Activities include implementation and Year 1 (Quarters [Q] 1 through 4) and Q5 operation, maintenance, and monitoring (OM&M) activities and performance monitoring results for the AS Interim Measure (IM) in the POL Southern Treatment Area, LTM results for the POL Northern Area and SW3, and supplemental direct push technology (DPT) sampling at both sites to support the LTM and performance monitoring programs. The timeframe for activities included in this report extends from August 2019 to August 2022. The scope for these sites currently includes two main components, which are documented within this report: (1) LTM at SW3 and POL Northern Area where an AS system began operation at these sites in May 2009 and June 2013, respectively, and subsequently turned off for both sites in March 2018 (during the previous reporting period); and (2) Active AS operations and performance monitoring in the POL Southern Treatment Area where an AS system was installed and began operation in 2021. The AS IM in the POL Southern Treatment Area was implemented between 2019 and 2021 to treat a chlorinated solvent groundwater plume that resulted from historic operations supporting the National Aeronautics and Space Administration’s (NASA) Space Program. The objective of the AS IM is to remediate groundwater within the treatment zone to support transition to monitored natural attenuation (MNA). The overall Corrective Action objective is to reduce concentrations of trichloroethene (TCE), cis-1,2-dichloroethene (cDCE), trans-1,2- dichloroethene (tDCE), and vinyl chloride (VC) present in groundwater to levels below their respective State of Florida Groundwater Cleanup Target Levels (GCTLs). The AS IM was installed in the POL Southern Treatment Area to target the high concentration plume (HCP), which includes a source zone (SZ) area where TCE was found to exceed 11,000 micrograms per liter (µg/L), and extend to a depth of 30 feet below land surface (bls).
This Year 2 Air Sparge (AS) System Performance Monitoring (PM) Report for Paint and Oil Locker (POL) Solid Waste Management Unit (SWMU) 067 Southern Treatment Area and Long- Term Monitoring (LTM) Report for POL Northern Area (SWMU 067) and Supply Warehouse #3 (SW3) SWMU 088 documents ongoing remedial efforts at the POL and SW3 sites at Kennedy Space Center (KSC), Florida. The overall goal for these sites is to reduce concentrations of groundwater contaminants of concern (COCs), specifically trichloroethene (TCE), cis-1,2-dichloroethene (cDCE), trans-1,2-dichloroethene (tDCE) and vinyl chloride (VC), to below the State of Florida Groundwater Cleanup Target Levels (GCTLs). Remediation and reporting of POL and SW3 have been streamlined over the years due to the proximity of the two sites. The scope for these sites currently includes two main components: (1) LTM at SW3 and the POL Northern Area, where an AS system began operation in May 2009 (with expansion in December 2012) and June 2013, respectively, and subsequently turned off for both sites in March 2018 (NASA, 2019a); and (2) Active AS operations and PM in the POL Southern Treatment Area where an AS system was installed and began operation in 2021. The timeframe for activities covered under this report is from September 2022 to July 2023. Based on Year 2 system operation and PM results, the AS system at POL operated as designed and successfully met the performance objective of reducing VOCs to concentrations that support transition of the site from active remediation to long-term monitoring. The results from the samples collected from performance monitoring wells within the AS system ROI showed a significant decrease in COC concentrations since the baseline sampling event conducted in April 2020. Based on the Year 2 OM&M and monitoring results obtained from the POL Southern Treatment Area, the IM objective to reduce concentrations to below the LTM transition target concentrations for TCE, cDCE, tDCE, and VC has been achieved. LTM sampling events at SW3 were conducted in October 2022 and July 2023. LTM sampling was conducted at the POL Northern Area in October 2022, December 2022, March 2023, and July 2023. Analytical results from October 2022 and July 2023 generally indicate that concentrations of COCs have been stable or decreasing compared to the previous year. TCE remains greater than the NADC in one monitoring well (POL-MW0034S) and greater than the GCTL in one monitoring well (POL-MW0009S). Concentrations of cDCE were greater than the GCTL in one monitoring well (POL-MW0026S), and tDCE was non-detect or less than the GCTL in all monitoring wells sampled. VC was greater than the GCTL in four monitoring wells (MW0024, MW0025, MW0027, and MW0028) at SW3 and one monitoring well (MW0026S) at the POL Northern Area.
This Hot Spot (HS) Area 6 Air Sparge Expansion – Phase Three Implementation Work Plan (IWP) was prepared by Tetra Tech, Inc., for the National Aeronautics and Space Administration (NASA) under the Indefinite Delivery Indefinite Quantity Contract 80KSC019D0011-80KSC019F0067, for the implementation of an Air Sparging (AS) Interim Measure (IM) at Launch Complex 34 (LC34), located at Cape Canaveral Space Force Station (CCSFS), Florida. LC34 has been designated as Solid Waste Management Unit (SWMU) CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act (RCRA) operating permit. Expansion of the HS 6 IM will include installation of an additional 192 AS wells to depths of approximately 40 feet below land surface (bls) to remediate contaminated groundwater within two areas located west and northeast of the existing HS 6 AS treatment area. These areas were delineated via direct push technology investigations in September and October 2023. The expansion will target “hot spot” concentrations of cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC), which are the contaminants of concern in these areas with concentrations greater than 10-times Florida Department of Environmental Protection Natural Attenuation Default Concentrations. The highest cDCE and VC concentrations detected in the proposed phase three expansion area were 58,000 micrograms per liter (μg/L) (32 to 36 feet bls) and 12,000 μg/L (23 to 27 feet bls), respectively. The objective for this expansion is to remediate contaminated groundwater within the treatment zone to support transition to long-term monitoring. This phase three expansion will add an additional 9.4 acres of treatment area to the HS 6 IM, which currently covers approximately 26.9 acres.
Here, we report the first hydrogel with the strength and modulus of cartilage in both tension and compression, and the first to exhibit cartilage-equivalent tensile fatigue strength at 100 000 cycles. These properties are achieved by infiltrating a bacterial cellulose (BC) nanofiber network with a poly(vinyl alcohol) (PVA)–poly(2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt) (PAMPS) double network hydrogel. The BC provides tensile strength in a manner analogous to collagen in cartilage, while the PAMPS provides a fixed negative charge and osmotic restoring force similar to the role of aggrecan in cartilage. The hydrogel has the same aggregate modulus and permeability as cartilage, resulting in the same time-dependent deformation under confined compression. The hydrogel is not cytotoxic, has a coefficient of friction 45% lower than cartilage, and is 4.4 times more wear-resistant than a PVA hydrogel. The properties of this hydrogel make it an excellent candidate material for replacement of damaged cartilage.
For the first time, direct evidence of graphene-induced molecular reorientation in polymer films using polarization modulated infrared reflection absorption spectroscopy (PMIRRAS) are presented. By creating favorable electrostatic interactions, graphene-polymer interfaces can be controlled by varying polymer and solvent composition. After trans of unmodified graphene from copper onto a polymer substrate, polymer chain rearrangement relative to the orientation at the polymer-copper interface is observed using PM-IRRAS. Transfer success is characterized using both optical transmission measurements and Raman spectroscopy to quantify the transfer fidelity, i.e. graphene coverage fraction. Taken together, oxygencontaining poly(ethylene-co-vinyl acetate) shows more polymer chain rearrangement and better graphene coverage compared to oxygen-free polyethylene. Polymer composition seems to dominate graphene-polymer interactions while solvent choice has a smaller effect on transfer quality. These results are the first direct measurement of this effect and point towards the possibility of engineering graphene-polymer interactions for specific applications.
Abstract Extracellular electron transfer (EET) denotes the process of microbial respiration with electron transfer to extracellular acceptors and has been exploited in a range of microbial electrochemical systems (MESs). To further understand EET and to optimize the performance of MESs, a better understanding of the dynamics at the microscale is needed. However, the real‐time monitoring of EET at high spatiotemporal resolution would require sophisticated signal amplification. To amplify local EET signals, a miniaturized bioelectronic device, the so‐called organic microbial electrochemical transistor (OMECT), is developed, which includes Shewanella oneidensis MR‐1 integrated onto organic electrochemical transistors comprising poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) combined with poly(vinyl alcohol) (PVA). Bacteria are attached to the gate of the transistor by a chronoamperometric method and the successful attachment is confirmed by fluorescence microscopy. Monitoring EET with the OMECT configuration is achieved due to the inherent amplification of the transistor, revealing fast time‐responses to lactate. The limits of detection when using microfabricated gates as charge collectors are also investigated. The work is a first step toward understanding and monitoring EET in highly confined spaces via microfabricated organic electronic devices, and it can be of importance to study exoelectrogens in microenvironments, such as those of the human microbiome.
Ethylene carbonate (EC) is an important component in state-of-the-art electrolytes for lithium-ion batteries (LIBs). However, EC is highly susceptible to oxidation on the surface of high-nickel layered oxide cathodes, making it undesirable for next-generation high-energy-density LIBs. In this study, a simple, yet effective, EC-free electrolyte (20F1.5M-1TDI) is presented by adding 20 wt% fluoroethylene carbonate (FEC) and 1 wt% lithium 4,5-dicyano-2-(trifluoromethyl)imidazole (LiTDI) into 1.5 M LiPF 6 in an ethyl methyl carbonate (EMC) electrolyte. The 20F1.5M-1TDI electrolyte is found to efficiently passivate the graphite anode and stabilize high-nickel cathodes by a synergistic decomposition of FEC and LiTDI. The LiNi 0.9 Mn 0.05 Al 0.05 O 2 (NMA90)/graphite full cell with the 20F1.5M-1TDI electrolyte, therefore, exhibits an enhanced cycling stability and a suppressed voltage hysteresis growth compared to that with an EC-containing baseline electrolyte (1 M LiPF 6 in EC:EMC, 3:7 in weight, with 2 wt% vinyl carbonate). Advanced analytical tools, such as time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy, are employed to understand the underlying working mechanism of the EC-free electrolyte. Furthermore, the present study clearly showcases the great potential of EC-free electrolytes as a straightforward, practical approach for LIBs with high-nickel cathodes.
Abstract Ionomers in the catalyst layer play a critical role in the performance of fuel cells and electrolyzers. Phenyl adsorption on hydrogen oxidation catalysts and electrochemical oxidation of phenyl moieties on oxygen evolution catalysts are detrimental to the alkaline devices’ performance. Here the adsorption energy of phenyl‐containing ionomers is compared to provide the rationale for implementing phenyl‐free ionomers. Density functional theory calculations indicated that the norbornane fragment has minimal adsorption energy on Pt(111) due to the absence of aromatic π electrons. A soluble quaternized polynorbornene ionomer is prepared by vinyl addition polymerization, and it exhibits high performance in both fuel cells and electrolyzers, proving the advantage of the phenyl‐free structure. This study establishes the phenyl adsorption energy‐electrode performance relationship, highlighting the importance of material interactions between the catalysts and ionomers.
Abstract Polyethylene terephthalate (PET) is selectively depolymerized by a carbon‐supported single‐site molybdenum‐dioxo catalyst to terephthalic acid (PTA) and ethylene. The solventless reactions are most efficient under 1 atmosphere of H 2 . The catalyst exhibits high stability and can be recycled multiple times without loss of activity. Waste beverage bottle PET or a PET + polypropylene (PP) mixture (simulating the bottle + cap) proceeds at 260 °C with complete PET deconstruction and quantitative PTA isolation. Mechanistic studies with a model diester, 1,2‐ethanediol dibenzoate, suggest the reaction proceeds by initial retro‐hydroalkoxylation/β‐C−O scission and subsequent hydrogenolysis of the vinyl benzoate intermediate.
Abstract The silylium‐like surface species [ i Pr 3 Si][(R F O) 3 Al−OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar−N=CMeMeC=N−Ar, Ar=2,6‐bis(diphenylmethyl)‐4‐methylbenzene) by chloride ion abstraction to form [(N^N)Pd−CH 3 ][(R F O) 3 Al−OSi≡)] ( 1 ). A combination of FTIR, solid‐state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S‐REDOR experiments are consistent with a weakly coordinated ion‐pair between (N^N)Pd−CH 3 + and [(R F O) 3 Al−OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd−CH 3 ] + in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.
Abstract Biomaterials such as spider silk and mussel byssi are fabricated by the dynamic manipulation of intra‐ and intermolecular biopolymer interactions. Organisms modulate solution parameters, such as pH and ion co‐solute concentration, to effect these processes. These biofabrication schemes provide a conceptual framework to develop new dynamic and responsive abiotic soft material systems. Towards these ends, the chemical diversity of readily available ionic compounds offers a broad palette to manipulate the physicochemical properties of polyelectrolytes via ion‐specific interactions. In this study, we show for the first time that the ion‐specific interactions of biomimetic polyelectrolytes engenders a variety of phase separation behaviors, creating dynamic thermal‐ and ion‐responsive soft matter that exhibits a spectrum of physical properties, spanning viscous fluids to viscoelastic and viscoplastic solids. These ion‐dependent characteristics are further rendered general by the merger of lysine and phenylalanine into a single, amphiphilic vinyl monomer. The unprecedented breadth, precision, and dynamicity in the reported ion‐dependent phase behaviors thus introduce a broad array of opportunities for the future development of responsive soft matter; properties that are poised to drive developments in critical areas such as chemical sensing, soft robotics, and additive manufacturing.
The silylium-like surface species [ i Pr 3 Si][(R F O) 3 Al-OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar-N=CMeMeC=N-Ar, Ar=2,6-bis(diphenylmethyl)-4-methylbenzene) by chloride ion abstraction to form [(N^N)Pd-CH 3 ][(R F O) 3 Al-OSi≡)] ( 1 ). A combination of FTIR, solid-state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S-REDOR experiments are consistent with a weakly coordinated ion-pair between (N^N)Pd-CH 3 + and [(R F O) 3 Al-OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd-CH 3 ] + in solution and incorporates up to 0.4% methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.
Abstract Flexible organic linkers represent an intuitive and effective strategy to design flexible metal–organic materials. We report herein a systematic study concerning the effect of varying the central bond of mixed pyridyl‐benzoate linkers, L, upon the flexibility of three isostructuralkddtopology microporous coordination networks (CNs) of formula ML 2 :X‐kdd‐1‐Cu,1= L = (E)‐4‐(pyridin‐4‐yldiazenyl)benzoate;X‐kdd‐2‐Cu,2= L = (E)‐4‐(2‐(pyridin‐4‐yl)vinyl)benzoate; the previously reportedX‐kdd‐3‐Cu,3= L = 4‐(pyridin‐4‐ylethynyl)benzoate. As revealed by single crystal x‐ray diffraction (SCXRD) and gas sorption studies,X‐kdd‐1‐Cu, exhibited gate‐opening during CO 2 and hydrocarbon (C2 and C8) sorption experiments whereas the other two CNs did not. Insight into these phase transformations was gained from in situ variable‐pressure and variable temperature powder X‐ray diffraction (PXRD), SCXRD, and modeling. Rotation of ligand1around the diazo bond, torsion angle changes between phenyl and carboxylate moieties, and deformation of the Cu‐based rod building blocks enabled activatedX‐kdd‐1‐Cuto form new phases with C8 isomers and CH 2 Cl 2 , CH 2 Cl 2 inducing contraction of the activated phase. Computational studies suggest that1enables flexibility thanks to its lower barrier of deformation versus2or3. This study teaches that diazo moieties could offer a general strategy to enhance the flexibility of CNs.
Adhesives are important in creating multilayer products, such as in packaging and construction. Most current hot-melt adhesives such as poly(ethylene-co-vinyl acetate) (EVA) and polyurethanes lack chemical recyclability and do not easily de-bond, complicating recycling. Here, we achieved tunable adhesive properties of chemically recyclable polyolefin-like multiblock copolymers through regulating the incorporation of crystalline hard blocks, amorphous soft blocks, and ester content highlighted by adhesive strengths up to 6.80 MPa. We further demonstrated applications of these adhesives in multi-layer films and showed that the adhesives can be readily de-bonded, recovered, and chemically recycled. Overall, this study into structure-property relationships, including effects of crystallinity, soft-block incorporation, and ester content of the multiblock copolymers on adhesive properties, has resulted in a modular hot-melt adhesive platform that exhibits chemical recyclability for virgin-quality adhesive re-generation, reprocessability for repeated reuse of the recovered adhesive, and tunability for designing adhesives with a wide range of low to high (up to ~80% stronger than EVA) adhesion strengths.