Removal of Lipophilic Wood Extractives from TMP Process Waters by Wet Oxidation

Työssä tutkittiin kokeellisesti rasvaliukoisten uuteaineiden poistamista TMP -prosessin vesikierroista märkähapetuksen avulla. Työn tavoitteena oli tutkia mahdollisuudet hyödyntää TMP -prosessissa vallitsevaa korkeaa lämpötilaa rasvaliukoisten uuteaineiden poistamiseen hapettamalla niitä puhtaalla hapella. Kirjallisuusosassa tarkasteltiin märkähapetuksen teknologiaa, reaktiomekanismia, käytettyjä katalyyttejä, käyttökohteita sekä kustannuksia. Kokeita suoritettiin autoklaavireaktorissa lämpötiloissa 140 °C, 160 °C ja 180 °C. Vetyperoksidia käytettiin katalyyttinä lisätyn vetyperoksidin määrän ollessa 100 - 1800 mg/l ja hapen osapaineen ollessa 0 ( typpiatmosfääri) - 15 baria. Kokeissa tarkasteltiin kemiallisen hapenkulutuksen (COD), rasvaliukoisten uuteaineiden konsentraation, orgaanisen kokonaishiilen (TOC) ja värin muutoksia kokeiden aikana eri lämpötiloilla, hapen osapaineilla ja lisätyn vetyperoksidin määrillä. Kokeissa saavutettiin 30 %:n COD:n vähenemä sekä 90 %:n vähenemä rasvaliukoisissa uuteaineissa lämpötiloissa 160 °C ja 180 °C. Lisäämällä vetyperoksidia katalyyttinä saavutettiin lähes sama tulos lämpötilassa 140 °C. Suurin tässä työssä havaittu ongelma oli lisääntynyt värinmuodostus vedessä olevassa hienojakoisessa kiintoaineessa hapetuksen aikana. Tämän vuoksi lisätutkimukset ovat tarpeellisia sen seikan selvittämiseksi, voidaanko muodostunut väri mahdollisesti poistaa massan valkaisussa.

Hot wire configuration for depositing device grade nano-crystalline silicon at high deposition rate

The University of Barcelona is developing a pilot-scale hot wire chemical vapor deposition (HW-CVD) set up for the deposition of nano-crystalline silicon (nc-Si:H) on 10 cm × 10 cm glass substrate at high deposition rate. The system manages 12 thin wires of 0.15-0.2 mm diameter in a very dense configuration. This permits depositing very uniform films, with inhomogeneities lower than 2.5%, at high deposition rate (1.5-3 nm/s), and maintaining the substrate temperature relatively low (250 °C). The wire configuration design, based on radicals' diffusion simulation, is exposed and the predicted homogeneity is validated with optical transmission scanning measurements of the deposited samples. Different deposition series were carried out by varying the substrate temperature, the silane to hydrogen dilution and the deposition pressure. By means of Fourier transform infrared spectroscopy (FTIR), the evolution in time of the nc-Si:H vibrational modes was monitored. Particular importance has been given to the study of the material stability against post-deposition oxidation.

Progress in single junction microcrystalline silicon solar cells deposited by Hot-Wire CVD

Hot-Wire Chemical Vapor Deposition has led to microcrystalline silicon solar cell efficiencies similar to those obtained with Plasma Enhanced CVD. The light-induced degradation behavior of microcrystalline silicon solar cells critically depends on the properties of their active layer. In the regime close to the transition to amorphous growth (around 60% of amorphous volume fraction), cells incorporating an intrinsic layer with slightly higher crystalline fraction and [220] preferential orientation are stable after more than 7000 h of AM1.5 light soaking. On the contrary, solar cells whose intrinsic layer has a slightly lower crystalline fraction and random or [111] preferential orientation exhibit clear light-induced degradation effects. A revision of the efficiencies of Hot-Wire deposited microcrystalline silicon solar cells is presented and the potential efficiency of this technology is also evaluated.

Surface passivation of crystalline silicon by Cat-CVD amorphous and nanocrystalline thin silicon films

In this work, we study the electronic surface passivation of crystalline silicon with intrinsic thin silicon films deposited by Catalytic CVD. The contactless method used to determine the effective surface recombination velocity was the quasi-steady-state photoconductance technique. Hydrogenated amorphous and nanocrystalline silicon films were evaluated as passivating layers on n- and p-type float zone silicon wafers. The best results were obtained with amorphous silicon films, which allowed effective surface recombination velocities as low as 60 and 130 cms -1 on p- and n-type silicon, respectively. To our knowledge, these are the best results ever reported with intrinsic amorphous silicon films deposited by Catalytic CVD. The passivating properties of nanocrystalline silicon films strongly depended on the deposition conditions, especially on the filament temperature. Samples grown at lower filament temperatures (1600 °C) allowed effective surface recombination velocities of 450 and 600 cms -1 on n- and p-type silicon.

Wet Oxidation of TMP Concentrated Paper Mill Process Water. Kinetics of the reaction

Työn tarkoituksena oli tutkia lämpötilan, paineen, pH:n ja katalyytin vaikutusta paperitehtaan TMP-konsentroidun prosessiveden märkähapetuksessa. Teoriaosio sisältää katsauksen sellu- ja paperiteollisuuteen, jätevesien käsittelyyn, nanosuodatuksen ja märkähapetusprosessin toimintaperiaatteet ja sovellukset hybriditeknologialle nanosuodatus-märkähapetuksessa. Empiirinen osa koostuu märkähapetuskokeista eri lämpötiloissa, paineissa, pH:ssa ja eri katalyyseillä. Työssä tutkittiin näiden vaikutusta kemialliseen hapenkulutukseen (COD), Biologiseen hapenkulutukseen (BOD), Välittömästi saatavana olevan biologisen hapenkulutukseen (IABOD), ligniiniin, täysin orgaanisen hiileen (TOC) ja rasvaliukoisten uuteaineiden (LWEs) pitoisuuteen. Tuloksina kokeellisesta työstä saatiin korkeimmat COD:n alenemat ja BOD/COD (biohajoavuus) suurimmilla lämpötilaolosuhteilla (COD:n alenema 70 % ja BOD/COD 97 % 200 °C:ssa ja hapen 10 bar osapaineella). Tutkimuksessa, jossa selvitettiin hapen osapaineen vaikutusta saatiin tuloksena, että hapen osapaineen kasvu parantaa orgaanisen kuormituksen poistoa: COD poisto oli olosuhteilla130°C, 5bar 5 %, olosuhteilla 130 °C, 15bar 15 %, olosuhteilla 170 °C, 5bar 20 % ja olosuhteilla 170 °C, 15bar 50 %. Lähes täydellinen LWEs –poisto saavutettiin 150 °C ja 10bar olosuhteilla, vaikka tässä lämpötilassa ei saavutettu korkeata orgaanisen kuormituksen poistoa. Emäksinen pH vaikutti suosivan hapettavia reaktioita, koska korkein COD:n poisto saavutettiin näissä olosuhteilla; kuitenkin alkalisen väliaineen tehokkuudelle löydettiin tärkeä lämpötilariippuvuus.

Tailoring the surface density of silicon nanocrystals embedded in SiOx single layers

In this article, we explore the possibility of modifying the silicon nanocrystal areal density in SiOx single layers, while keeping constant their size. For this purpose, a set of SiOx monolayers with controlled thickness between two thick SiO2 layers has been fabricated, for four different compositions (x=1, 1.25, 1.5, or 1.75). The structural properties of the SiO x single layers have been analyzed by transmission electron microscopy (TEM) in planar view geometry. Energy-filtered TEM images revealed an almost constant Si-cluster size and a slight increase in the cluster areal density as the silicon content increases in the layers, while high resolution TEM images show that the size of the Si crystalline precipitates largely decreases as the SiO x stoichiometry approaches that of SiO2. The crystalline fraction was evaluated by combining the results from both techniques, finding a crystallinity reduction from 75% to 40%, for x = 1 and 1.75, respectively. Complementary photoluminescence measurements corroborate the precipitation of Si-nanocrystals with excellent emission properties for layers with the largest amount of excess silicon. The integrated emission from the nanoaggregates perfectly scales with their crystalline state, with no detectable emission for crystalline fractions below 40%. The combination of the structural and luminescence observations suggests that small Si precipitates are submitted to a higher compressive local stress applied by the SiO2 matrix that could inhibit the phase separation and, in turn, promotes the creation of nonradiative paths.

Stability of hydrogenated nanocrystalline silicon thin-film transistors

Hydrogenated nanocrystalline silicon thin-films were obtained by catalytic chemical vapour deposition at low substrate temperatures (150°C) and high deposition rates (10 Å/s). These films, with crystalline fractions over 90%, were incorporated as the active layers of bottom-gate thin-film transistors. The initial field-effect mobilities of these devices were over 0.5 cm 2/V s and the threshold voltages lower than 4 V. In this work, we report on the enhanced stability of these devices under prolonged times of gate bias stress compared to amorphous silicon thin-film transistors. Hence, they are promising candidates to be considered in the future for applications such as flat-panel displays.

Optoelectronic studies in nanocrystalline silicon Schottky diodes obtained by Hot-Wire Chemical Vapour Deposition

The very usual columnar growth of nanocrystalline silicon leads to electronic transport anisotropies. Whereas electrical measurements with coplanar electrodes only provide information about the electronic transport parallel to the substrate, it is the transverse transport which determines the collection efficiency in thin film solar cells. Hence, Schottky diodes on transparent electrodes were obtained by hot-wire CVD in order to perform external quantum efficiency and surface photovoltage studies in sandwich configuration. These measurements allowed to calculate a transverse collection length, which must correlate with the photovoltaic performance of thin film solar cells. Furthermore, the density of charge trapped at localized states in the bandgap was estimated from the voltage dependence of the depletion capacitance of these rectifying contacts.

Aluminium fouling and its impact on activated carbon based dioxin and furan removal in a wet scrubber at a co-incineration plant

Dioxins and furans, PCDD/Fs, are highly toxic substances formed in post combustion zones in furnaces. PCDD/F emissions are regulated by a waste incineration directive which relates also to co-incineration plants. Several observations of dioxin and furan enhancements in wet scrub- bers have been reported previously. This is thought to be due to the so-called "memory effect" which occurs when dioxins and furans absorb into plastic material in scrubbers and desorb when ambient circumstances alter significantly. At the co-incineration plant involved, dioxins and furans are controlled with a wet scrubber, the tower packing of which is made of plastic in which activated carbon particles are dispersed. This should avoid the memory effect and act as a dioxin and furan sink since dioxins and furans are absorbed irreversibly into the packing ma- terial. In this case, the tower packing in the scrubber is covered with a white layer that has been found to be mainly aluminium. The aim of this thesis was to determine the aluminium balance and the dioxin and furan behaviour in the scrubber and, thus, the impacts that the foul- ing has on dioxin and furan removal. The source of aluminium, reasons for fouling and further actions to minimize its impacts on dioxin and furan removal were also to be discovered. Measurements in various media around the scrubber and in fuels were made and a profile analysis of PCDD/F and mass balance calculations were carried out. PCDD/F content de- creased in the scrubber. The reduced PCDD/F was not discharged into scrubbing water. The removal mechanism seems to work in spite of the fouling, at least with low PCDD/F loads. Most of the PCDD/F in excess water originates from the Kymijoki River which is used as feeding water in the scrubber. Fouling turned out to consist mainly of aluminium hydroxides. Sludge combusted in the furnace was found to be a significant source of aluminium. Ways to minimize the fouling would be adjustment of pH to a proper lever, installation of a mechanical filter to catch the loose material from the scrubbing water and affecting the aluminium content of the sludge.

Amorphous silicon thin film solar cells deposited entirely by Hot-Wire Chemical Vapour Deposition at low temperature (<150 ºC)

Amorphous silicon n-i-p solar cells have been fabricated entirely by Hot-Wire Chemical Vapour Deposition (HW-CVD) at low process temperature < 150 °C. A textured-Ag/ZnO back reflector deposited on Corning 1737F by rf magnetron sputtering was used as the substrate. Doped layers with very good conductivity and a very less defective intrinsic a-Si:H layer were used for the cell fabrication. A double n-layer (μc-Si:H/a-Si:H) and μc-Si:H p-layer were used for the cell. In this paper, we report the characterization of these layers and the integration of these layers in a solar cell fabricated at low temperature. An initial efficiency of 4.62% has been achieved for the n-i-p cell deposited at temperatures below 150 °C over glass/Ag/ZnO textured back reflector.

Electronic transport in low temperature nanocrystalline silicon thin-film transistors obtained by Hot-Wire CVD

Hydrogenated nanocrystalline silicon (nc-Si:H) obtained by hot-wire chemical vapour deposition (HWCVD) at low substrate temperature (150 °C) has been incorporated as the active layer in bottom-gate thin-film transistors (TFTs). These devices were electrically characterised by measuring in vacuum the output and transfer characteristics for different temperatures. The field-effect mobility showed a thermally activated behaviour which could be attributed to carrier trapping at the band tails, as in hydrogenated amorphous silicon (a-Si:H), and potential barriers for the electronic transport. Trapped charge at the interfaces of the columns, which are typical in nc-Si:H, would account for these barriers. By using the Levinson technique, the quality of the material at the column boundaries could be studied. Finally, these results were interpreted according to the particular microstructure of nc-Si:H.

Microcrystalline silicon thin film transistors obtained by Hot-Wire CVD

Polysilicon thin film transistors (TFT) are of great interest in the field of large area microelectronics, especially because of their application as active elements in flat panel displays. Different deposition techniques are in tough competition with the objective to obtain device-quality polysilicon thin films at low temperature. In this paper we present the preliminary results obtained with the fabrication of TFT deposited by hot-wire chemical vapor deposition (HWCVD). Some results concerned with the structural characterization of the material and electrical performance of the device are presented.

Top-gate microcrystalline silicon TFTs processed at low temperature (<200ºC)

N-type as well P-type top-gate microcrystalline silicon thin film transistors (TFTs) are fabricated on glass substrates at a maximum temperature of 200 °C. The active layer is an undoped μc-Si film, 200 nm thick, deposited by Hot-Wire Chemical Vapor. The drain and source regions are highly phosphorus (N-type TFTs) or boron (P-type TFTs)-doped μc-films deposited by HW-CVD. The gate insulator is a silicon dioxide film deposited by RF sputtering. Al-SiO 2-N type c-Si structures using this insulator present low flat-band voltage,-0.2 V, and low density of states at the interface D it=6.4×10 10 eV -1 cm -2. High field effect mobility, 25 cm 2/V s for electrons and 1.1 cm 2/V s for holes, is obtained. These values are very high, particularly the hole mobility that was never reached previously.

Microdoping compensation of microcrystalline silicon obtained by Hot-Wire Chemical Vapour Deposition

Undoped hydrogenated microcrystalline silicon was obtained by hot-wire chemical vapour deposition at different silane-to-hydrogen ratios and low temperature (<300 °C). As well as technological aspects of the deposition process, we report structural, optical and electrical characterizations of the samples that were used as the active layer for preliminary p-i-n solar cells. Raman spectroscopy indicates that changing the hydrogen dilution can vary the crystalline fraction. From electrical measurements an unwanted n-type character is deduced for this undoped material. This effect could be due to a contaminant, probably oxygen, which is also observed in capacitance-voltage measurements on Schottky structures. The negative effect of contaminants on the device was dramatic and a compensated p-i-n structure was also deposited to enhance the cell performance.

New features of the layer-by-layer deposition of microcrystalline silicon films revealed by spectroscopic ellipsometry and high resolution transmission electron microscopy

Spectroscopic ellipsometry and high resolution transmission electron microscopy have been used to characterize microcrystalline silicon films. We obtain an excellent agreement between the multilayer model used in the analysis of the optical data and the microscopy measurements. Moreover, thanks to the high resolution achieved in the microscopy measurements and to the improved optical models, two new features of the layer-by-layer deposition of microcrystalline silicon have been detected: i) the microcrystalline films present large crystals extending from the a-Si:H substrate to the film surface, despite the sequential process in the layer-by-layer deposition; and ii) a porous layer exists between the amorphous silicon substrate and the microcrystalline silicon film.