Resolving the relative contributions of cistern and pour flushing to toilet water usage: Measurements from urban test sites in India.

A challenge in water reuse for toilet flushing in India and other Asian countries derives from pour flushing practices. It is a common assumption that the amount of pour flushed water used for personal cleansing is small in comparison to the cistern flush volume, however there is a knowledge gap regarding the actual contribution of each water source to the blackwater amount. In this study, digital water meters were used to measure the fraction of water from personal wash tap relative to cistern water that is used for toilet flushing. High temporal resolution measurements were carried in three different urban sites in the city of Coimbatore in the southern Indian state of Tamil Nadu where onsite sanitation treatment prototypes that may provide reclaimed water for cistern flushing are being tested. Data collected over periods of up to 2 months show that the contribution of the cistern flush to the total blackwater volume is low (14-40%). These data highlight an important factor to inform interventions designed around water reuse for flushing in world geographies where personal toilet cleansing by water is the common practice.

Remediation of suspended solids and turbidity by improved settling tank design in a small-scale, free-standing toilet system using recycled blackwater.

Our research is focused on the development of decentralized waste water treatment technologies enabling onsite water reuse. Accumulation of solids with recycling of treated blackwater increases the energy required for disinfection with an electrochemical process. We hypothesized that improving the preprocess settling of blackwater by increasing the tortuosity of the liquid flow path would reduce this energy demand by reducing particle-associated chemical oxygen demand (COD). This approach successfully reduced the total suspended solids and turbidity in the process liquid accumulated per user-day equivalent. A modest reduction in the apparent steady-state accumulation of COD was also observed, likely because of the retention of COD associated with larger particles in the settling tanks. Interestingly, these improvements did not improve the energy efficiency of the electrochemical disinfection process, as predicted. These observations suggest that improving the energy efficiency of electrochemical disinfection will require remediation of dissolved COD.

Electrochemical disinfection of repeatedly recycled blackwater in a free-standing, additive-free toilet.

Decentralized, energy-efficient waste water treatment technologies enabling water reuse are needed to sustainably address sanitation needs in water- and energy-scarce environments. Here, we describe the effects of repeated recycling of disinfected blackwater (as flush liquid) on the energy required to achieve full disinfection with an electrochemical process in a prototype toilet system. The recycled liquid rapidly reached a steady state with total solids reliably ranging between 0.50 and 0.65% and conductivity between 20 and 23 mS/cm through many flush cycles over 15 weeks. The increase in accumulated solids was associated with increased energy demand and wide variation in the free chlorine contact time required to achieve complete disinfection. Further studies on the system at steady state revealed that running at higher voltage modestly improves energy efficiency, and established running parameters that reliably achieve disinfection at fixed run times. These results will guide prototype testing in the field.

Enhanced H2O2 Production at Reductive Potentials from Oxidized Boron-Doped Ultrananocrystalline Diamond Electrodes.

This work investigates the surface chemistry of H2O2 generation on a boron-doped ultrananocrystalline diamond (BD-UNCD) electrode. It is motivated by the need to efficiently disinfect liquid waste in resource constrained environments with limited electrical power. X-ray photoelectron spectroscopy was used to identify functional groups on the BD-UNCD electrode surfaces while the electrochemical potentials of generation for these functional groups were determined via cyclic voltammetry, chronocoulometry, and chronoamperometry. A colorimetric technique was employed to determine the concentration and current efficiency of H2O2 produced at different potentials. Results showed that preanodization of an as-grown BD-UNCD electrode can enhance the production of H2O2 in a strong acidic environment (pH 0.5) at reductive potentials. It is proposed that the electrogeneration of functional groups at oxidative potentials during preanodization allows for an increased current density during the successive electrolysis at reductive potentials that correlates to an enhanced production of H2O2. Through potential cycling methods, and by optimizing the applied potentials and duty cycle, the functional groups can be stabilized allowing continuous production of H2O2 more efficiently compared to static potential methods.

Influence of Veneering Fabrication Techniques and Gas-Phase Fluorination on Bond Strength between Zirconia and Veneering Ceramics.

PURPOSE: Porcelain chipping has been one of the main problems of porcelain-fused-to-zirconia restorations. This study evaluates the bond strengths of layered, pressed, and adhesively bonded porcelain to yttria-stabilized zirconia substrates that have undergone traditional preparation or gas-phase fluorination. MATERIALS AND METHODS: A three-point bending test was used to evaluate the bond strength of the porcelain and zirconia interface. Sixty-six specimens were prepared (n = 11) following ISO 9693 and loaded until failure using an Instron testing machine. One-half of the zirconia substrates received gas phase fluorination treatment before veneering application. Three porcelain veneering methods were evaluated: layered, pressed, and adhesively bonded porcelain. Bond strength results were interpreted using a two-way ANOVA and a Bonferroni multiple comparisons test. Statistical significance was set at α = 0.05. RESULTS: ANOVA revealed a statistically significant effect of the veneering fabrication methods. No main effect was observed regarding the surface treatment to the zirconia. There was a significant effect related to the veneering method used to apply porcelain to zirconia. For untreated zirconia, layered porcelain had a significantly higher flexural strength compared to pressed or bonded, while pressed and bonded porcelains were not significantly different from one another. For zirconia specimens receiving fluorination treatment, both layered and pressed porcelains had significantly higher bond strengths than adhesively bonded porcelain. In addition, fluorinated pressed porcelain was not statistically different from the control layered or fluorinated layered porcelain. CONCLUSION: The choice of veneering fabrication technique was critical when evaluating the zirconia to porcelain interfacial bond strength. Bonded porcelain to zirconia had a lower flexural strength than layered or pressed porcelain, regardless of zirconia surface treatment. In addition, fluorination had an effect on the bond strength of pressed porcelain.

Chemical ionization mass spectrometry using carbon nanotube field emission electron sources.

A novel chemical ionization (CI) source has been developed based on a carbon nanotube (CNT) field emission electron source. The CNT-based electron source was evaluated and compared with a standard filament thermionic electron source in a commercial explosives trace detection desktop mass spectrometer. This work demonstrates the first reported use of a CNT-based ion source capable of collecting CI mass spectra. Both positive and negative modes were investigated. Spectra were collected for a standard mass spectrometer calibration compound, perfluorotributylamine (PFTBA), as well as trace explosives including trinitrotoluene (TNT), Research Department explosive (RDX), and pentaerythritol tetranitrate (PETN). The electrical characteristics, lifetime at operating pressure, and power requirements of the CNT-based electron source are reported. The CNT field emission electron sources demonstrated an average lifetime of 320 h when operated in constant emission mode under elevated CI pressures. The ability of the CNT field emission source to cycle on and off can provide enhanced lifetime and reduced power consumption without sacrificing performance and detection capabilities. Graphical Abstract ᅟ.

Evidence of yttrium silicate inclusions in YSZ-porcelain veneers.

This report introduces the discovery of crystalline defects that can form in the porcelain veneering layer when in contact with yttria-stabilized zirconia (YSZ). The focus was on dental prostheses and understanding the defects that form in the YSZ/porcelain system; however the data reported herein may have broader implications toward the use and stability of YSZ-based ceramics in general. Specimens were cut from fully sintered YSZ plates and veneering porcelain was applied (<1 mm thick) to one surface and fired under manufacturer's recommended protocol. Scanning electron microscopy (SEM) with integrated electron dispersive X-ray (EDAX) was used for microstructural and elemental analysis. EDAX, for chemical analysis and transmission electron diffraction (TED) for structural analysis were both performed in the transmission electron microscope (TEM). Additionally, in order to spatially resolve Y-rich precipitates, micro-CT scans were conducted at varying depths within the porcelain veneer. Local EDAX (SEM) was performed in the regions of visible inclusions and showed significant increases in yttrium concentration. TEM specimens also showed apparent inclusions in the porcelain and selected area electron diffraction was performed on these regions and found the inclusions to be crystalline and identified as either yttrium-silicate (Y2 SiO5 ) or yttrium-disilicate (Y2 Si2 O7 ). Micro-CT data showed that yttrium-silicate precipitates were distributed throughout the thickness of the porcelain veneer. Future studies are needed to determine whether many of the premature failures associated with this materials system may be the result of crystalline flaws that form as a result of high temperature yttrium diffusion near the surfaces of YSZ.

Fracture toughness improvements of dental ceramic through use of yttria-stabilized zirconia (YSZ) thin-film coatings.

OBJECTIVES: The aim of this study was to evaluate strengthening mechanisms of yttria-stabilized zirconia (YSZ) thin film coatings as a viable method for improving fracture toughness of all-ceramic dental restorations. METHODS: Bars (2mm×2mm×15mm, n=12) were cut from porcelain (ProCAD, Ivoclar-Vivadent) blocks and wet-polished through 1200-grit using SiC abrasive. A Vickers indenter was used to induce flaws with controlled size and geometry. Depositions were performed via radio frequency magnetron sputtering (5mT, 25°C, 30:1 Ar/O2 gas ratio) with varying powers of substrate bias. Film and flaw properties were characterized by optical microscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD). Flexural strength was determined by three-point bending. Fracture toughness values were calculated from flaw size and fracture strength. RESULTS: Data show improvements in fracture strength of up to 57% over unmodified specimens. XRD analysis shows that films deposited with higher substrate bias displayed a high %monoclinic volume fraction (19%) compared to non-biased deposited films (87%), and resulted in increased film stresses and modified YSZ microstructures. SEM analysis shows critical flaw sizes of 67±1µm leading to fracture toughness improvements of 55% over unmodified specimens. SIGNIFICANCE: Data support surface modification of dental ceramics with YSZ thin film coatings to improve fracture toughness. Increase in construct strength was attributed to increase in compressive film stresses and modified YSZ thin film microstructures. It is believed that this surface modification may lead to significant improvements and overall reliability of all-ceramic dental restorations.

Surface fluorination of zirconia: adhesive bond strength comparison to commercial primers.

OBJECTIVE: This study evaluated contact angle and shear bond strength of three commercial zirconia primers and compared them to a recently developed fluorination pre-treatment. Earlier investigations reported that plasma fluorinated zirconia modifies the chemical bonding structure creating a more reactive surface. MATERIALS AND METHODS: Yttria-stabilized zirconia (LAVA, 3M ESPE) plates were highly polished using 3µm diamond paste (R(a) ∼200nm) prior to pretreatments. After primer and fluorination treatment, contact angles were measured to quantify surface hydrophobicity before and after ethanol clean. Additionally, simple shear bond tests were performed to measure the adhesion strength to a composite resin. RESULTS: Plasma fluorination produced the lowest contact angle (7.8°) and the highest shear bond strength (37.3MPa) suggesting this pretreatment facilitates a more "chemically" active surface for adhesive bonding. CONCLUSIONS: It is hypothesized that plasma fluorination increase hydroxylation at the surface, making it more reactive, thus allowing for covalent bonding between zirconia surface and resin cement. A strong correlation was observed between contact angle and adhesion strength for all specimens; a relationship which may help understand the frequency and modes of failures, clinically. It is also believed that this surface treatment can increase long-term viability of zirconia restorations over other adhesive techniques.

Critical appraisal. Resin bonding to zirconia.

Research has focused on adhesion and bond strengths to zirconia, but the question is "what is the gold standard--what is the bond strength we are trying to achieve?" Clinical data are needed to further understand adhesion issues--and studies are just now being published. Preliminary clinical research indicates that some failures are due to loss of adhesion but more are due to chipping of veneer porcelain. Commercial adhesion products are continuously being developed and optimized for clinical use. It is anticipated that the use of zirconia in dentistry will increase in the future, so reliable clinical adhesion solutions are needed. Based on the literature and the commercial products available to clinicians today, using novel primers (e.g., Z-PrimePlus) coupled with low pressure air-abrasion would be more than sufficient for adequate bonding of resin cement.

Long-term microtensile bond strength of surface modified zirconia.

OBJECTIVE: To compare long-term microtensile bond strength of zirconia, surface-modified via a novel treatment, to current surface conditioning methods for zirconia, when resin bonded to dental composite. METHODS: Two ProCAD (porcelain) and 10 sintered ZirCAD (ZrO(2)) blocks (18 mm × 14 mm × 12 mm) were obtained from manufacturers. Twelve Herculite XRV composite blocks were fabricated (18 mm × 14 mm × 12 mm). Bonding surface of blocks was polished through 1200-grit SiC and air-abraded (50 µm alumina, 0.28MPa, 20s). Blocks were then separated into six groups: (1) porcelain (control), HF-etched/silane-treated, (2) ZrO(2), tribochemical-coated/silane-treated, (3) ZrO(2), primer-treated, (4) ZrO(2), modified via novel 3.2 nm silica layer/silane-treated, (5) ZrO(2), modified via novel 5.8nm silica layer/silane-treated, and (6) ZrO(2), modified via novel 30.4 nm silica layer/silane-treated. Blocks were bonded to composite using Clearfil Esthetic cement. Blocks were stored in distilled water (37°C, 24h), then cut into microtensile bars (n=8/gp), then bond strengths were measured using a universal testing machine at 0, 1, 3, and 6 months. All groups were statistically analyzed (ANOVA, Tukey's, p<0.05). RESULTS: At 6 months (aging), all silica seed layer specimens displayed microtensile bond strength similar to CoJet specimens but less than that of silane-modified dental porcelain. CONCLUSION: The deposition of a silica layer on zirconia resulted in similar or superior long-term resin bond strength when compared to traditional silanation and bonding techniques for zirconia but lower than that for silane-treated dental porcelain.

A novel array chip to monitor in situ composite degradation using electrochemical impedance spectroscopy.

OBJECTIVES: This paper presents a novel array-chip technology used to monitor the physical properties of dental composites in situ. The DECAY chip (Degradation via Electrochemical Array) leverages microfabrication techniques to construct a uniform array of recessed wells that may be filled with dental restorative materials (e.g. composite or amalgam) and analyzed electrochemically in solution. METHODS: The array enables the uniform preparation of multiple specimens and reference controls on a common substrate, all of which may be simultaneously evaluated. The DECAY-chip presented here consists of a 3 × 3 array of 100 µm deep wells, and is used to monitor the degradation of a common dental composite as a function of time. RESULTS: The data correlate changes in the measured dielectric properties to surface and bulk changes as the composite is exposed to an ethanol:DI mixture (75% ethanol). A model for the system is presented, as are future plans to simplify the methodology for rapid materials screening and in vitro analyses. SIGNIFICANCE: This in situdiagnostic chip will enable evaluation of composite specimens, tested under a wide range of simulated oral environments. It may also serve as a screening platform for new composite formulations and aid in the study of materials degradation and failure mechanisms.

Enhanced bonding between YSZ surfaces using a gas-phase fluorination pretreatment.

The present investigation focuses on the surface modification, via gas-phase fluorination process, of yttria- stabilized zirconia (YSZ) to increase its wettability and chemical bonding directly to acrylate-based resin cements. YSZ plates and cylinders, as-received and roughened, were pretreated in a fluorine containing plasma and bonded with a commercially available resin cement for simple shear bond adhesion testing. No organo-silane coupling agent was used to enhance bonding between the two substrates. Shear bond tests revealed that bond strength increased with fluorination time. Furthermore, the pretreated, as received (nonroughened) specimen group displayed relatively high bond strengths suggesting surface reactivity and direct chemical bonding with the resin cement. X-ray photoelectron spectroscopy analysis revealed the surface conversion layer to be a mixture of phases; zirconium oxyfluoride, zirconium fluoride, and yttrium fluoride. It is hypothesized that these fluoride and oxyfluoride phases have the potential to increase surface hydroxylation, enabling direct covalent bonding between YSZ and resin cement. It is believed that this surface treatment has broad reaching impact when using high-strength ceramics in a multitude of bioapplications.

Development of a novel surface modification for improved bonding to zirconia.

OBJECTIVE: This report presents a novel pretreatment technique, whereby the zirconia surface is converted to a more reactive zirconium oxyfluoride, enabling improved chemical bonding to other dental substrates via conventional silanation approaches. METHODS: The study leverages a novel gas-phase fluorination process that creates a thin oxyfluoride conversion layer on the surface of zirconia, making it more reactive for conventional adhesive bonding techniques. Zirconia specimens, polished and roughened, were pretreated and composite cylinders bonded using conventional adhesive techniques. All specimens were subjected to a force at a crosshead speed of 0.5mm/min in an electro-mechanical testing device. Single-factor analysis of variance (ANOVA) at a 5% confidence level was performed for the bonding strength data. Optical microscopy and scanning electron microscopy (SEM) were used to evaluate and quantify failure surfaces. RESULTS: Shear bond strengths were analyzed using single-factor ANOVA (p<0.05). Mechanical testing results revealed that fluorinated zirconia specimens (both rough and polished) displayed the highest shear bond strengths as compared to other commercially available treatments. X-ray photoelectron spectroscopy analysis helped determine that this novel pretreatment created a more reactive, 2-4nm thick oxyfluoride conversion layer with approximate stoichiometry, ZrO(3)F(4). CONCLUSION: Simple shear bond mechanical tests demonstrated that a fluorination pre-treatment is a viable method to chemically modify zirconia to produce a reactive surface for adhesive bonding.

Adhesion/cementation to zirconia and other non-silicate ceramics: where are we now?

Non-silicate ceramics, especially zirconia, have become a topic of great interest in the field of prosthetic and implant dentistry. A clinical problem with use of zirconia-based components is the difficulty in achieving suitable adhesion with intended synthetic substrates or natural tissues. Traditional adhesive techniques used with silica-based ceramics do not work effectively with zirconia. Currently, several technologies are being utilized clinically to address this problem, and other approaches are under investigation. Most focus on surface modification of the inert surfaces of high strength ceramics. The ability to chemically functionalize the surface of zirconia appears to be critical in achieving adhesive bonding. This review will focus on currently available approaches as well as new advanced technologies to address this problem.

Dynamic fatigue behavior of dental porcelain modified by surface deposition of a YSZ thin film.

PURPOSE: The objective of this study was to evaluate the basic fatigue parameters of a dental porcelain modified by deposition of a yttria-stabilized zirconia (YSZ) thin film and to compare the data to that of an unmodified control. METHODS: Two hundred bars (2 x 2 x 15 mm(3)) were cut from ProCAD blocks. Specimens were wet-polished with 1200-grit SiC abrasive. One surface of each bar was sandblasted with 50 microm Al2O3 abrasive (50 psi). Half the specimens were further modified through deposition of a 3-microm YSZ thin film on the sandblasted surface. Depositions were performed using an radio frequency magnetron sputter system (working pressure of 15 mT, 150 degrees C, 30:1 Ar:O2 gas ratio). Specimens were tested at different stressing rates: 5.0, 0.1, and 0.01 MPa/s (n = 25/group) in deionized water (37 degrees C), and inert strength was determined in air (25 degrees C, 70 MPa/s). All strength measurements were carried out by three-point bending (span = 10 mm) in a servo-electric test system. RESULTS: The mean flexural strength values (MPa) and standard deviation for the uncoated sandblasted group were: 98.6 (5.5), 90.7 (5.9), and 84.2 (8.5), and for the sandblasted + YSZ thin film group: 125 (9.4), 119.3 (7.8), and 102.8 (7.0), for the highest to the lowest stressing rates, respectively. The fatigue parameters n and lnB were calculated by linear regression of dynamic fatigue data. For the uncoated group, n = 38 and lnB = 4.7 MPa(2)/s, and for the coated group, n = 33 and lnB = 10.8 MPa(2)/s. Weibull analysis was also performed showing that the characteristic parameter (sigma(o)) was 113.3 and 125.7 MPa for the uncoated and coated group, respectively. CONCLUSIONS: There was an increase in strength for specimens modified by application of a YSZ thin film. It is hypothesized that thin-film application modifies flaws or residual surface stress states.

Effect of YSZ thin film coating thickness on the strength of a ceramic substrate.

Although ceramics are used for many different biomedical applications they are brittle materials that can be compromised by surface defects when under stress. The objective of this study was to evaluate the effect of surface modification with an yttria-stabilized zirconia (YSZ) thin film coating on the strength of a machinable dental ceramic. Fifty bars (2 mm x 2 mm x 15 mm) were cut from ProCAD (Ivoclar-Vivadent) blocks. Specimens were wet-polished through 1200-grit SiC abrasive. One surface of each bar was sandblasted with 50 microm Al(2)O(3) abrasive (0.34 MPa). Specimens were further modified through the deposition of a sputtered YSZ thin film on the sandblasted surface. Different thin film thicknesses were evaluated: 1, 3, 5, and 7 microm. Depositions were performed using a radio frequency magnetron sputter system (working pressure of 15 mT, 150 degrees C, 30:1 Ar/O(2) gas ratio). Flexural strength measurements were carried out by three-point bending (span = 10 mm) in a servo-electric material testing system in DI water (37 degrees C). The results showed that the strength of porcelain significantly increased with the deposition of a 3-microm YSZ thick coating. A nonlinear relationship was observed between film thickness and strength. Strengthening of porcelain is shown through the application of a sputtered YSZ thin film. It is presumed that the strengthening mechanism is due to modification of surface flaws and/or surface residual stress by the applied thin film.

Dynamic fatigue and strength characterization of three ceramic materials.

Fracture strength and fatigue parameters of three ceramic materials submitted to dynamic fatigue were evaluated. A machinable leucite-reinforced dental ceramic, aluminum oxide, and yttria-stabilized zirconia (YSZ) were tested. The inert strength of the materials was determined in air (25 degrees C) at stressing rates of 70, 250, 400 MPa/s for Porcelain, Alumina and YSZ respectively. The data was analyzed using a two-parameter Weibull distribution. The Weibull modulus (m) and the characteristic of fracture (sigma0) parameters were determined for each material. Specimens were also tested in 3-point bending at different stressing rates in distilled/deionized water at 37 degrees C (dynamic fatigue) in order to calculate the fatigue parameters n and ln B. The strength for each material was characterized using Strength-Probability-Time (SPT) diagrams for 1 day, 1 year and 10 years. YSZ showed a high-fracture strength sigma0 (1,459 MPa) at a failure probability of 63.2% and high resistance to subcritical crack growth. YSZ and alumina showed better resistance to slow crack growth than porcelain, indicating less susceptibility to strength degradation by stress corrosion. Lifetime predictions after 10 years indicate a reduction of 50%, 36% and 29% in strength for porcelain, alumina and YSZ respectively. YSZ seems to be a very promising material for long-term dental and biomedical applications.

In vitro toothbrush-dentifrice abrasion of two restorative composites.

BACKGROUND: Surface wear can be a problem with directly placed composites. PURPOSE: This study evaluated the in vitro wear and surface roughness of two composites at different cycle intervals after being subjected to toothbrush-dentifrice abrasion. MATERIALS AND METHODS: Twenty specimens of a microhybrid, Filtek Z250 (3M ESPE, St. Paul, MN, USA), and a nanofill composite, Filtek Supreme (3M ESPE), were prepared according to the manufacturer's directions. Each specimen was subjected to toothbrush-dentifrice abrasion (250 g vertical load) using a deionized water-dentifrice slurry (Close-Up, Lever Ponds Ltd., La Lucia, ZA) and toothbrush heads (Oral-B 40, Oral-B Laboratories, Delmont, CA, USA). A brushing sequence of 10,000, 20,000, 50,000, and 100,000 strokes was performed for all samples at a rate of 1.5 Hz. At baseline and each cycle interval, a surface profilometer was used to determine average surface roughness, Ra. At the same intervals, vertical loss of material was measured with a precision micrometer. Data were analyzed using repeated-measures analysis of variance at p value .05. Analyses with atomic force microscopy (AFM) and scanning electron microscopy (SEM) were also performed. RESULTS: After 20,000, 50,000, and 100,000 cycles, Filtek Supreme showed less significant wear than Z250. Filtek Supreme demonstrated higher surface roughness than Z250 after 50,000 and 100,000 cycles. However, AFM and SEM images indicated a more uniform surface topography for Filtek Supreme than for Z250. Abrasion wear and surface roughness increased with each cycle interval for both materials. CONCLUSIONS: Although the initial performance of both materials was similar, a greater number of brushing cycles revealed differences between the wear resistance and generated surface roughness of the materials. CLINICAL SIGNIFICANCE: The wear resistance and roughness results of Filtek Supreme suggest that it is suitable for clinical use, mainly in areas that are more subject to abrasive wear, such as Class V restorations.