Aerosol Jet Printing of Graphene and Carbon Nanotube Patterns on Realistically Rugged Substrates.

Direct-write additive manufacturing of graphene and carbon nanotube (CNT) patterns by aerosol jet printing (AJP) is promising for the creation of thermal and electrical interconnects in (opto)electronics. In realistic application scenarios, this however often requires deposition of graphene and CNT patterns on rugged substrates such as, for example, roughly machined and surface-oxidized metal block heat sinks. Most AJP of graphene/CNT patterns has thus far however concentrated on flat wafer- or foil-type substrates. Here, we demonstrate AJP of graphene and single walled CNT (SWCNT) patterns on realistically rugged plasma-electrolytic-oxidized (PEO) Al blocks, which are promising heat sink materials. We show that AJP on the rugged substrates offers line resolution of down to ∼40 µm width for single AJP passes, however, at the cost of noncomplete substrate coverage including noncovered µm-sized pores in the PEO Al blocks. With multiple AJP passes, full coverage including coverage of the pores is, however, readily achieved. Comparing archetypical aqueous and organic graphene and SWCNT inks, we show that the choice of the ink system drastically influences the nanocarbon AJP parameter window, deposit microstructure including crystalline quality, compactness of deposit, and inter/intrapass layer adhesion for multiple passes. Simple electrical characterization indicates aqueous graphene inks as the most promising choice for AJP-deposited electrical interconnect applications. Our parameter space screening thereby forms a framework for rational process development for graphene and SWCNT AJP on application-relevant, rugged substrates.

Multiscale optical simulation settings: challenging applications handled with an iterative ray-tracing FDTD interface method.

We show that with an appropriate combination of two optical simulation techniques-classical ray-tracing and the finite difference time domain method-an optical device containing multiple diffractive and refractive optical elements can be accurately simulated in an iterative simulation approach. We compare the simulation results with experimental measurements of the device to discuss the applicability and accuracy of our iterative simulation procedure.

Multiple interfacing between classical ray-tracing and wave-optical simulation approaches: a study on applicability and accuracy.

In this study the applicability of an interface procedure for combined ray-tracing and finite difference time domain (FDTD) simulations of optical systems which contain two diffractive gratings is discussed. The simulation of suchlike systems requires multiple FDTD↔RT steps. In order to minimize the error due to the loss of the phase information in an FDTD→RT step, we derive an equation for a maximal coherence correlation function (MCCF) which describes the maximum degree of impact of phase effects between these two different diffraction gratings and which depends on: the spatial distance between the gratings, the degree of spatial coherence of the light source and the diffraction angle of the first grating for the wavelength of light used. This MCCF builds an envelope of the oscillations caused by the distance dependent coupling effects between the two diffractive optical elements. Furthermore, by comparing the far field projections of pure FDTD simulations with the results of an RT→FDTD→RT→FDTD→RT interface procedure simulation we show that this function strongly correlates with the error caused by the interface procedure.

The impact of the non-linearity of the radiant flux on the thermal load of the color conversion elements in phosphor converted LEDs under different current driving schemes.

For a systematic approach to improve the reliability and the white light quality of phosphor converted light-emitting diodes (LEDs) it is imperative to gain a better understanding of the individual parameters that affect color temperature constancy and maintenance. By means of a combined optical and thermal simulation procedure, in this contribution we give a comprehensive discussion on the impact of different current driving schemes on the thermal load of the color conversion elements (CCEs) of phosphor converted LEDs. We show that on the one hand a decreasing duty cycle under pulse width modulation driving conditions may cause a notable temperature variation and on the other hand also effects due to the non-linearity between the blue radiant flux and the current have to be considered for the thermal load of the CCEs.

Unresolved complex mixture (UCM) in coastal environments is derived from fossil sources.

The unresolved complex mixture (UCM) frequently dominates organic extracts isolated from estuarine and coastal sediments in the vicinity of industrial centers. Despite an obvious link to a petroleum source, speculation exists that biogenic sources also contribute to the UCM. To determine the source of the UCM to these environments, natural abundance radiocarbon (Δ(14)C) and stable carbon (δ(13)C) isotopic composition of the UCM solvent-extracted from coastal sediments, road dust, and urban atmospheric particulate in the United States was measured. Extracts of UCM and separate saturate and aromatic fractions from all samples are predominantly (>90%) fossil-derived and hence have a petroleum source. Even the polar fraction of the UCM, which has a Δ(14)C composition reflecting contributions from recently photosynthesized carbon (-665‰), is composed of ~66% fossil carbon indicating the presence of petroleum residues that have been transformed into more polar derivatives. The δ(13)C of the UCM had consistent values (-27.65 ± 0.51‰; n = 16) for all but one sample, indicating a common origin of the UCM. We conclude that in coastal areas dominated by human activities whole fractions of the UCM, as well as separate saturate, aromatic, and polar fractions, are principally derived from petroleum sources.

Tribology of bio-inspired nanowrinkled films on ultrasoft substrates.

Biomimetic design of new materials uses nature as antetype, learning from billions of years of evolution. This work emphasizes the mechanical and tribological properties of skin, combining both hardness and wear resistance of its surface (the stratum corneum) with high elasticity of the bulk (epidermis, dermis, hypodermis). The key for combination of such opposite properties is wrinkling, being consequence of intrinsic stresses in the bulk (soft tissue): Tribological contact to counterparts below the stress threshold for tissue trauma occurs on the thick hard stratum corneum layer pads, while tensile loads smooth out wrinkles in between these pads. Similar mechanism offers high tribological resistance to hard films on soft, flexible polymers, which is shown for diamond-like carbon (DLC) and titanium nitride thin films on ultrasoft polyurethane and harder polycarbonate substrates. The choice of these two compared substrate materials will show that ultra-soft substrate materials are decisive for the distinct tribological material. Hierarchical wrinkled structures of films on these substrates are due to high intrinsic compressive stress, which evolves during high energetic film growth. Incremental relaxation of these stresses occurs by compound deformation of film and elastic substrate surface, appearing in hierarchical nano-wrinkles. Nano-wrinkled topographies enable high elastic deformability of thin hard films, while overstressing results in zigzag film fracture along larger hierarchical wrinkle structures. Tribologically, these fracture mechanisms are highly important for ploughing and sliding of sharp and flat counterparts on hard-coated ultra-soft substrates like polyurethane. Concentration of polyurethane deformation under the applied normal loads occurs below these zigzag cracks. Unloading closes these cracks again. Even cyclic testing do not lead to film delamination and retain low friction behavior, if the adhesion to the substrate is high and the initial friction coefficient of the film against the sliding counterpart low, e.g. found for DLC.

Hemocompatibility of Inorganic Physical Vapor Deposition (PVD) Coatings on Thermoplastic Polyurethane Polymers.

Biocompatibility improvements for blood contacting materials are of increasing interest for implanted devices and interventional tools. The current study focuses on inorganic (titanium, titanium nitride, titanium oxide) as well as diamond-like carbon (DLC) coating materials on polymer surfaces (thermoplastic polyurethane), deposited by magnetron sputtering und pulsed laser deposition at room temperature. DLC was used pure (a-C:H) as well as doped with silicon, titanium, and nitrogen + titanium (a-C:H:Si, a-C:H:Ti, a-C:H:N:Ti). In-vitro testing of the hemocompatibility requires mandatory dynamic test conditions to simulate in-vivo conditions, e.g., realized by a cone-and-plate analyzer. In such tests, titanium- and nitrogen-doped DLC and titanium nitride were found to be optimally anti-thrombotic and better than state-of-the-art polyurethane polymers. This is mainly due to the low tendency to platelet microparticle formation, a high content of remaining platelets in the whole blood after testing and low concentration of platelet activation and aggregation markers. Comparing this result to shear-flow induced cell motility tests with e.g., Dictostelium discoideum cell model organism reveals similar tendencies for the investigated materials.

The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999.

Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.

Occurrence of polybrominated diphenyl ethers (PBDEs) in brown trout bile and liver from Swiss rivers.

The ranges of total polybrominated diphenyl ethers (PBDEs) in fish from four Swiss rivers were 0.8-240 ng/g in the bile and 16-7400 ng/g lipid in the liver. PBDE concentrations varied within each river and among the various rivers. Female fish tended to have higher concentrations in the liver, while the male fish had higher concentrations in the bile. From the resulting PBDE concentrations in fish it could not be infered that these contaminants contribute to the causes of the observed fish catch decline in Swiss rivers.

Non-invasive imaging of tissue PO2 in malignant melanoma of the skin.

In various tumor systems, decreased PO2 values have been demonstrated by various methods. This study addresses the question of whether tumor hypoxia can be found in cutaneous melanoma using lifetime imaging of non-invasive sensors showing phosphorescence quenched by oxygen. Twenty-three cases of cutaneous malignant melanoma (average tumor thickness 1.25 mm, range 0.5-8 mm) were examined using the SkinCam lifetime imaging system for the assessment of cutaneous PO2 levels within the tumors and in adjacent clinically normal skin. For comparison, 30 non-melanoma skin tumors were evaluated. In 15 exploitable melanoma cases, the average hypoxic difference of the lesion compared with the surrounding skin was -10 mmHg, typically associated with an inhomogeneous distribution. Only 10% of the non-melanoma lesions showed a similar hypoxia (false positives). The SkinCam equipment uses a non-invasive imaging method and provides further diagnostic hints in the assessment of benign and malignant skin tumors.

Benzotriazoles, alkylphenols and bisphenol A in municipal wastewaters and in the Glatt River, Switzerland.

BACKGROUND: Many organic micropollutants occur at trace concentrations in municipal wastewater effluents and in the aquatic environment. Some of these xenobiotic chemicals can be considered as 'emerging' contaminants and some are suspect to have endocrine disrupting effects. Among the latter are nonylphenol (NP), octylphenol (OP) and bisphenol A (BPA), which deserve special attention due to their ubiquitous occurrence in the aquatic environment. The complexing agents benzotriazole (BT) and tolyltriazole (TT) are applied as anticorrosive agents (e.g. in cooling and hydraulic fluids, in antifreezing fluids, in aircraft deicing fluids, in dish washing liquids for silver protection), as antifogging agents and as intermediates for the synthesis of various chemicals. The environmental occurrence of NP and OP is caused by the fact that they are intermediate products (metabolites) in the biodegradation of alkylphenol polyethoxylate surfactants. BPA is globally used for the production of polycarbonate and epoxy resins. METHODS: BT, TT, NP, OP and BPA were quantitatively determined in municipal wastewater effluents in Switzerland and in the Glatt River. The analytes were enriched by solid-phase enrichment. BT and TT were determined underivatized by electrospray LC/tandem MS. Reversed-phase LC was performed on octylsilica columns with isocratic water/methanol elution. Multiple reaction monitoring of the positive ions provided selective and sensitive detection for reliable quantifications. NP, OP and BPA were determined by GC/MS after derivatization with N-methyl-N-(trimethylsilyl)-trifluoroacetamide. RESULTS AND DISCUSSION: BT and TT concentrations in primary and secondary effluents of municipal wastewater treatment plants varied from below 10 to 100 microg/L. The ranges of the concentrations in the Glatt River in ng/L were 636-3,690 for BT, 122-628 for TT, 68-326 for NP, 6-22 for OP and 9-76 for BPA. The corresponding mass flows in g/d were 93-1,870 for BT, 18-360 for TT, 24-183 for NP, 1-16 for OP and 2-72 for BPA. The concentrations and mass flows of NP in the River Glatt were drastically lower than the analogous values found 15 years ago. Thus, a substantially decreased environmental exposure can be observed due to the reduction of the use of alkyphenol polyethoxylate surfactants in Switzerland. The current concentrations of NP, OP and BPA are within the ranges reported for weakly impacted surface waters. CONCLUSION: The investigated contaminants occur at quantitatively measurable but varying concentrations in municipal wastewaters and in the Glatt River reflecting their ubiquitous input into wastewaters and their different behaviour during biological wastewater treatment.

Anaerobic degradation of brominated flame retardants in sewage sludge.

Tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), and decabromodiphenyl ether (DecaBDE) are high production volume chemicals used as flame retardants in plastics for products such as electronic equipment, insulation panels, and textiles. The environmental safety of brominated flame retardants, especially their persistence, bioaccumulation, and toxicity is a controversial topic. Here, we studied and compared the degradation of TBBPA, HBCD, and DecaBDE under anaerobic conditions in digested sewage sludge. The half-lives of TBBPA and a technical HBCD mixture were 0.59 and 0.66 d, respectively. The fact that (+/-)-alpha-HBCD exhibited an almost doubled half-life compared to (+/-)-beta-HBCD and (+/-)-gamma-HBCD is an important finding with respect to the discussion on the persistence of individual HBCD stereoisomers and the recent reports on strong relative enrichment of alpha-HBCD in biota. We found no statistically significant enantioselective degradation of alpha-, beta-, or gamma-HBCD. Half-lives of TBBPA and a technical HBCD mixture were not dependent on the presence of additional nutrients or primers. Concentrations of TBBPA and a technical HBCD mixture decreased also in sterile control samples, however, at a rate that was more than a factor of 50 smaller than in incubations under non-sterile conditions. Compared to TBBPA and a technical HBCD mixture, DecaBDE exhibited a much longer half-life of 7 x 10(2)d in the same system. Pseudo-first-order degradation rate constants decreased according to the following sequence: TBBPA congruent with(+/-)-gamma-HBCD congruent with(+/-)-beta-HBCD>(+/-)-alpha-HBCD>>DecaBDE. Preliminary investigations suggest that degradation of TBBPA, HBCD, and DecaBDE occurs in full-scale anaerobic digesters, as well.

Depositional history of organic contaminants in Narragansett Bay, Rhode Island, USA.

Sediment cores were taken at three locations in Narragansett Bay, Rhode Island, USA in 1997 and analyzed for a variety of organic contaminants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), chlordanes, linear alkyl benzenes (LABs), benzotriazoles (BZTs) and dichlorodiphenyltrichloroethanes (DDTs) and metabolites. The distributions of these chemicals at Apponaug Cove and in the Seekonk River indicate that there was a disturbance in the depositional environment relative to cores collected at these locations in 1986 demonstrating the potential for buried contaminants to be remobilized in the environment even after a period of burial. Sharp breaks in the concentration of several organic markers with known dates of introduction were successfully used to determine the sedimentation rate at Quonset Point. Both the Quonset Point and Seekonk River cores had subsurface maximums for DDTs, PCBs, PAHs and BZTs, which are consistent with expected inputs to the environment. The Apponaug Cove core showed an increase of most contaminants at the surface indicating a recent event in which more contaminated sediments were deposited at that location.

Anaerobic degradation of decabromodiphenyl ether.

The environmental safety of decabromodiphenyl ether (BDE-209), a widely used flame retardant, has been the topic of controversial discussions during the past several years. Degradation of BDE-209 into lower brominated diphenyl ether congeners, exhibiting a higher bioaccumulation potential, has been a critical issue. Here, we report on the degradation of BDE-209 and the formation of octa- and nonabromodiphenyl ether congeners under anaerobic conditions. Sewage sludge collected from a mesophilic digester was used as the inoculum and incubated up to 238 days with and without a set of five primers. Following Soxhlet extraction and a liquid chromatography cleanup procedure, parent compounds and debromination products were analyzed by GC/HRMS. In experiments with primers, concentrations of BDE-209 decreased by 30% within 238 days. This corresponds to a pseudo-first-order degradation rate constant of 1 x 10(-3) d(-1). Without primers, the degradation rate constant was 50% lower. Formation of two nonabromodiphenyl ether and six octabromodiphenyl ether congeners proved that BDE-209 underwent reductive debromination in these experiments. Debromination occurred at the para and the meta positions, whereas debromination at the ortho position was not statistically significant. All three nonabromodiphenyl ether congeners (BDE-206, BDE-207, and BDE-208) were found to undergo reductive debromination as well. No significant change of the BDE-209 concentration and no formation of lower brominated congeners was observed in sterile control experiments. To our knowledge, this is the first report demonstrating microbially mediated reductive debromination of BDE-209 under anaerobic conditions.

Organophosphate flame retardants and plasticizers in indoor air.

Analytical methods were developed for a broad range of organophosphate flame retardants and plasticizers in indoor air. Screening was performed of various indoor environments at 12 locations in and around Zurich, Switzerland. Method recoveries ranged from 62% for triphenyl phosphate to 100% for tris(2-ethylhexyl) phosphate. Tris(2-chloro-isopropyl) phosphate was found in the highest concentration (260 ng/m(3)) mainly in cars and furniture stores. Tris(2-ethylhexyl) phosphate and triphenyl phosphate, both up to 3.4 ng/m(3), were also detected in quantifiable concentrations at several sites. Tris(1,3-dichloroisopropyl) phosphate, tricresyl phosphate and tri(2-butoxyethyl) phosphate were below the limit of quantification in all samples. The results of the risk assessment indicate that the observed concentrations are below the predicted threshold for human health effects.

Polychlorinated biphenyls in Narragansett Bay surface sediments.

Polychlorinated biphenyls (PCBs) were evaluated in 41 surface sediments collected from Narragansett Bay, RI in 1997-1998. Highest concentrations of total PCBs (1760 ng/g) were in rivers at the head of the bay and the values decreased southward toward the mouth of the bay, with elevated concentrations in some of the coves. The PCB levels in approximately 43% of the samples exceeded the effects range median (ERM) guideline [Environ. Manage. 19 (1995) 81] indicating possible adverse biological effects at these stations. Principal component analysis (PCA) of the surface sediment PCBs separated the Taunton River samples from the rest of the samples. This result suggests that this river has a different PCB composition and sources than the other areas investigated. It also showed that this river has a limited influence on other bay stations as the adjacent samples downstream did not have the same chemical signature. Congener ratios derived from the PCA were useful in distinguishing stations that had different sources of PCBs than the bulk of the bay sediments. Although Aroclor 1268 and 1270 accounted for <1% of all PCB production, their major components, CB206 and CB209, account for 3-6% of the CBs in most bay samples. This may reflect more local use of these Aroclor mixtures and/or be indicative of their relative stability, compared to less chlorinated mixtures. Using linear alkyl benzenes (LABs) as a marker for sewage derived PCBs suggested that up to 95% of the PCBs at the most contaminated sites in the Seekonk, Providence, and Taunton Rivers were sewage derived. This analysis also showed that there is a high background level (167 ng/g) of PCBs in the Seekonk and Providence River, while the Taunton River had a relatively low background level (23.7 ng/g). At the furthest stations south in the Providence River, the sewage derived PCBs only accounted for 23% of the total which suggests that PCB associated with sewage particles are rapidly deposited and are therefore not the most significant source of these compounds to the lower reaches of Narragansett Bay.

The distribution and sources of polycyclic aromatic hydrocarbons in Narragansett Bay surface sediments.

Polycyclic aromatic hydrocarbons (PAHs) were measured in 41 surface sediments from Narragansett Bay, RI. All the analytes generally decrease down bay from the Seekonk, Providence and Taunton Rivers at the head of the bay. Total PAHs ranged from 0.569 to 216 microg/g with 27% exceeding the effects range median (ERM) of 44.8 microg/g and 73% of the stations exceeding the effects range low (ERL) of 4.02 microg/g (Long et al., 1995). Based on principal component analysis, the major source of the contaminants in Narragansett Bay was the Providence River while the coves and Taunton River/Mt. Hope Bay appeared to only have a limited influence on the open bay. PAH source ratios indicate that creosote and/or coal may be the most significant contributor of pyrogenic high molecular weight PAHs in Narragansett Bay, along with significant contributions from diesel exhaust.

Partial analytical solution of a model used for measuring oxygen diffusion coefficients of polymer films by luminescence quenching.

Many aspects of optical chemical sensor design would benefit from a better knowledge of the diffusion properties of the analyte in the polymer host. The response times of such sensors to a step change of analyte concentration are of vital interest for many applications of fast-responding sensors. Further, the diffusion properties govern their quenching behavior and their sensitivity. A method for determination of the diffusion constant of oxygen in polymers has been developed and used by several groups in the past. The underlying mathematical model for luminescence quenching by molecules of a gas in a single sensing layer on an impermeable support has not yet been completely derived in an analytical form and still uses tedious numerical methods. We present a partial analytical solution to the problem of modeling the time dependence of luminescence generated by in- or out-diffusion of a gaseous quencher in a polymer film in which a luminophor is immobilized and offer a suitable method to predict sensor response times.