Random mixtures with orientational order, and the anisotropic resistivity tensor of high Tc superconductors

By generalizing effective-medium theory to the case of orientationally ordered but positionally disordered two component mixtures, it is shown that the anisotropic dielectric tensor of oxide superconductors can be extracted from microwave measurements on oriented crystallites of YBa2Cu3O7¿x embedded in epoxy. Surprisingly, this technique appears to be the only one which can access the resistivity perpendicular to the copper¿oxide planes in crystallites that are too small for depositing electrodes. This possibility arises in part because the real part of the dielectric constant of oxide superconductors has a large magnitude. The validity of the effective-medium approach for orientationally ordered mixtures is corroborated by simulations on two¿dimensional anisotropic random resistor networks. Analysis of the experimental data suggests that the zero-temperature limit of the finite frequency resistivity does not vanish along the c axis, a result which would simply the existence of states at the Fermi surface, even in the superconducting state

Modelling plant species distribution in alpine grasslands using airborne imaging spectroscopy.

Remote sensing using airborne imaging spectroscopy (AIS) is known to retrieve fundamental optical properties of ecosystems. However, the value of these properties for predicting plant species distribution remains unclear. Here, we assess whether such data can add value to topographic variables for predicting plant distributions in French and Swiss alpine grasslands. We fitted statistical models with high spectral and spatial resolution reflectance data and tested four optical indices sensitive to leaf chlorophyll content, leaf water content and leaf area index. We found moderate added-value of AIS data for predicting alpine plant species distribution. Contrary to expectations, differences between species distribution models (SDMs) were not linked to their local abundance or phylogenetic/functional similarity. Moreover, spectral signatures of species were found to be partly site-specific. We discuss current limits of AIS-based SDMs, highlighting issues of scale and informational content of AIS data.

Ab initio valence-bond cluster model for ionic solids: Alkaline-earth oxides

A linear M-O-M (M=metal, O=oxygen) cluster embedded in a Madelung field, and also including the quantum effects of the neighboring ions, is used to represent the alkaline-earth oxides. For this model an ab initio wave function is constructed as a linear combination of Slater determinants written in an atomic orbital basis set, i.e., a valence-bond wave function. Each valence-bond determinant (or group of determinants) corresponds to a resonating valence-bond structure. We have obtained ab initio valence-bond cluster-model wave functions for the electronic ground state and the excited states involved in the optical-gap transitions. Numerical results are reasonably close to the experimental values. Moreover, the model contains the ionic model as a limiting case and can be readily extended and improved.

Chiroptical measurement of chiral aggregates at liquid-liquid interface in centrifugal liquid membrane cell by Mueller matrix and conventional circular dichroism methods

The centrifugal liquid membrane (CLM) cell has been utilized for chiroptical studies of liquid-liquid interfaces with a conventional circular dichroism (CD) spectropolarimeter. These studies required the characterization of optical properties of the rotating cylindrical CLM glass cell, which was used under the high speed rotation. In the present study, we have measured the circular and linear dichroism (CD and LD) spectra and the circular and linear birefringence (CB and LB) spectra of the CLM cell itself as well as those of porphyrine aggregates formed at the liquid-liquid interface in the CLM cell, applying Mueller matrix measurement method. From the results, it was confirmed that the CLM-CD spectra of the interfacial porphyrin aggregates observed by a conventional CD spectropolarimeter should be correct irrespective of LD and LB signals in the CLM cell.

Role of structural saturation and geometry in the luminescence of silicon-based nanostructured materials

The structural saturation and stability, the energy gap, and the density of states of a series of small, silicon-based clusters have been studied by means of the PM3 and some ab initio (HF/6-31G* and 6-311++G**, CIS/6-31G* and MP2/6-31G*) calculations. It is shown that in order to maintain a stable nanometric and tetrahedral silicon crystallite and remove the gap states, the saturation atom or species such as H, F, Cl, OH, O, or N is necessary, and that both the cluster size and the surface species affect the energetic distribution of the density of states. This research suggests that the visible luminescence in the silicon-based nanostructured material essentially arises from the nanometric and crystalline silicon domains but is affected and protected by the surface species, and we have thus linked most of the proposed mechanisms of luminescence for the porous silicon, e.g., the quantum confinement effect due to the cluster size and the effect of Si-based surface complexes.

Photonic characteristics of Langmuir-Blodgett self-assembled monolayers of colloidal silica particles

Monodispersed colloidal crystals based on silica sub-micrometric particles were synthesized using the Stöber-Fink-Bohn process. The control of nucleation and coalescence result in improved characteristics such as high sphericity and very low size dispersion. The resulting silica particles show characteristics suitable for self-assembling across large areas of closely-packed 2D crystal monolayers by an accurate Langmuir-Blodgett deposition process on glass, fused silica and silicon substrates. Due to their special optical properties, colloidal films have potential applications in fields including photonics, electronics, electro-optics, medicine (detectors and sensors), membrane filters and surface devices. The deposited monolayers of silica particles were characterized by means of FESEM, AFM and optical transmittance measurements in order to analyze their specific properties and characteristics. We propose a theoretical calculation for the photonic band gaps in 2D systems using an extrapolation of the photonic behavior of the crystal from 3D to 2D. In this work we show that the methodology used and the conditions in self-assembly processes are decisive for producing high-quality two-dimensional colloidal crystals by the Langmuir-Blodgett technique.

Cadmium-free quantum dots in aqueous solution: potential for fingermark detection, synthesis and an application to the detection of fingermarks in blood on non-porous surfaces

The use of quantum dots (QDs) in the area of fingermark detection is currently receiving a lot of attention in the forensic literature. Most of the research efforts have been devoted to cadmium telluride (CdTe) quantum dots often applied as powders to the surfaces of interests. Both the use of cadmium and the nano size of these particles raise important issues in terms of health and safety. This paper proposes to replace CdTe QDs by zinc sulphide QDs doped with copper (ZnS:Cu) to address these issues. Zinc sulphide-copper doped QDs were successfully synthesized, characterized in terms of size and optical properties and optimized to be applied for the detection of impressions left in blood, where CdTe QDs proved to be efficient. Effectiveness of detection was assessed in comparison with CdTe QDs and Acid Yellow 7 (AY7, an effective blood reagent), using two series of depletive blood fingermarks from four donors prepared on four non-porous substrates, i.e. glass, transparent polypropylene, black polyethylene and aluminium foil. The marks were cut in half and processed separately with both reagents, leading to two comparison series (ZnS:Cu vs. CdTe, and ZnS:Cu vs. AY7). ZnS:Cu proved to be better than AY7 and at least as efficient as CdTe on most substrates. Consequently, copper-doped ZnS QDs constitute a valid substitute for cadmium-based QDs to detect blood marks on non-porous substrates and offer a safer alternative for routine use.

Up-conversion effect of Er- and Yb-doped ZnO thin films

Visible up-conversion in ZnO:Er and ZnO:Er:Yb thin films deposited by RF magnetron sputtering under different O2-rich atmospheres has been studied. Conventional photoluminescence (325 nm laser source) and up-conversion (980 nm laser source) have been performed in the films before and after an annealing process at 800 °C. The resulting spectra demonstrate that the thermal treatment, either during or post-deposition, activates optically the Er3+ ions, being the latter process much more efficient. Moreover, the atmosphere during deposition was also found to be an important parameter, as the deposition under O2 flow increases the optical activity of Er+3 ions. In addition, the inclusion of Yb3+ ions into the films has shown an enhancement of the visible up-conversion emission at 660 nm by a factor of 4, which could be associated to either a better energy transfer from the 2F5/2 Yb level to the 4I11/2 Er one, or to the prevention of having Er2O3 clustering in the films.

Current transport and electroluminescence mechanisms in thin SiO2 films containing Si nanocluster-sensitized erbium ions.

We have studied the current transport and electroluminescence properties of metal oxide semiconductor MOS devices in which the oxide layer, which is codoped with silicon nanoclusters and erbium ions, is made by magnetron sputtering. Electrical measurements have allowed us to identify a Poole-Frenkel conduction mechanism. We observe an important contribution of the Si nanoclusters to the conduction in silicon oxide films, and no evidence of Fowler-Nordheim tunneling. The results suggest that the electroluminescence of the erbium ions in these layers is generated by energy transfer from the Si nanoparticles. Finally, we report an electroluminescence power efficiency above 10−3%. © 2009 American Institute of Physics. doi:10.1063/1.3213386

ZnO nanorods for efficient third harmonic UV generation.

ZnO nanorods grown by both high temperature vapour phase transport and low temperature chemical bath deposition are very promising sources for UV third harmonic generation. Material grown by both methods show comparable efficiencies, in both cases an order of magnitude higher than surface third harmonic generation at the quartz-air interface of a bare quartz substrate. This result is in stark contrast to the linear optical properties of ZnO nanorods grown by these two methods, which show vastly different PL efficiencies. The third harmonic generated signal is analysed using intensity dependent measurements and interferometric frequency resolved optical gating, allowing extraction of the laser pulse parameters. The comparable levels of efficiency of ZnO grown by these very different methods as sources for third harmonic UV generation provides a broad suite of possible growth methods to suit various substrates, coverage and scalability requirements. Potential application areas range from interferometric frequency resolved optical gating characterization of few cycle fs pulses to single cell UV irradiation for biophysical studies.

Hienopaperimassojen lujuusominaisuudet nopeassa vetokuormituksessa

Työssä verrattiin koivu-, akaasia- ja eucalyptussellujen käyttökelpoisuutta hienopapereiden kuituraaka-aineena. Kirjallisuusosassa todettiin radan hallinnan paperikoneiden avoimissa vienneissä riippuvan käytetyn geometrian lisäksi lujuus- ja relaksaatio-ominaisuuksista. Kuituverkoston käyttäytymiseen jännityksen alaisena vaikuttavat kuitudimensiot, kosteus ja lämpötila sekä kuituverkostoon kohdistetun jännityksen nopeus ja määrä. Relaksaationopeus ja vetolujuus kasvavat kuivilla papereilla vetonopeuden lisääntyessä. Kosteuspitoisuuden kasvattaminen alentaa puukuiduissa olevien polymeerien lasisiirtymälämpötilaa, jonka seurauksena vetolujuus ja relaksaatiokireys laskevat voimakkaasti. Kosteuspitoisuuden kasvaessa murtovenymä kasvaa lähes lineaarisesti ja repäisylujuus sekä murtotyö saavuttavat maksiminsa tietyssä kosteuspitoisuudessa. Kokeellisessa osassa keskityttiin hienopaperimassojen lujuus- ja relaksaatiokäyttäytymisen selvittämiseen nopeassa vetokuormituksessa. Lisäksi määritettiin laatu-, massa- ja rakenneominaisuuksia valituille koepisteille. Muuttujina kokeissa olivat massojen kuiva-ainepitoisuudet ja jauhatusolosuhteet sekä havusellun osuus hienopaperimassoissa.CSF-tasoon 350 ml jauhetuista näytteistä parhaat lujuus ja relaksaatio-ominaisuudet olivat koivulla ja heikoimmat akaasialla. Erot koepisteiden välillä korostuivat pienellä havusellun määrällä, mutta kaventuivat huomattavasti havusellun määrää lisättäessä. Samaan vetolujuuteen jauhettaessa massojen erot poistuvat kokonaan. Kuivilla näytteillä löydettiin erinomainen korrelaatio myötölujuuden ja relaksaatiokireyden välille. Puristinkuivien näytteiden relaksaatiokireyksiä voidaan kokeiden valossa ennustaa parhaiten kuivien näytteiden vetolujuuksista. Myös elastisten venymien osuuksille ja kuituseinämien paksuuksille löydettiin selvä yhteys.Eucalyptus- ja akaasiamassojen erinomaisuus hienopapereiden raaka-aineena korostui niiden optisissa ominaisuuksissa, erityisesti korkeana valonsirontana. Verrattaessa samassa vetolujuudessa ja relaksaatiokireydessä valonsirontakertoimien arvoja havaittiin akaasian olevan paras koivun jäädessä heikoimmaksi. Lisäksi akaasian ja eucalyptuksen kapeat kuitujakaumat ovat edullisia painokoneessa värin tasaisen imeytymisen kannalta. Akaasian pienet ja taipuisat kuidut antavat paperille tasaisen pinnan ja siten painatuksessa tasaisen painoalustan.

Hiokerejektien käsittely MC-sakeudessa

Työn tavoitteena oli optimoida LWC-paperitehtaan kahden hiomolinjan rejektinkäsittelyt. Uusituilla rejektilinjoilla on käytössä keskisakeusrejektinjauhatus. Työn keskeinen osa oli teräkoeajot, teräsarjoja tutkittiin kuusi, kolme molemmilla linjoilla. Kahdessa ensimmäisessä teräkoeajossa oli molemmilla linjoilla samanlaiset jauhinterät. Teräkoeajojen tuloksista havaittiin yleisellä tasolla, että suurin osa mitatuista ominaisuuksista parani jauhatusastetta nostettaessa. Ainoastaan repäisylujuus heikkeni. Terävaihtoehdoista pystyttiin poimimaan molemmille linjoille sopiva terävaihtoehto. Rejektinlajittelun havaittiin parantavan edelleen massan laatuominaisuuksia, paitsi repäisylujuutta. Toisena osuutena vertailtiin keskisakeusjauhimen terävaihtoehtoa, jolla saavutettiin hyviä tuloksia, toisen paperitehtaan korkeassa sakeudessa jauhettuun rejektiin. Korkeasakeusjauhimen terää ei erityisesti valikoitu koeajoa varten. Tuloksista havaittiin, että keskisakeusjauhimella saadaan aikaan varsin hyvää LWC-paperiin käytettävää massaa. Keskisakeudessa jauhettu massa oli monilta ominaisuuksiltaan jopa parempaa kuin korkeasakeusjauhimen massa. Työn kolmannessa osuudessa ajettiin rejektilinjalla sakeuskoeajo. Sakeuskoeajosta havaittiin, että optiset ominaisuudet olivat parhaimmillaan jauhimen MC-sakeusalueen keskivaiheilla. Jauhatussakeuden noustessa kuidut jäivät jäykemmiksi ja karkeammiksi. Tikkupitoisuus oli sitä pienempi, mitä alhaisempaa jauhatussakeutta käytettiin. Sakeudella ei ollut selvää vaikutusta lujuusominaisuuksiin. Tulosten perusteella paras jauhatussakeus keskisakeusjauhimella oli sakeusalueen puoliväli. Työn viimeisenä osana selvitettiin miten kytkentämuutos, jossa rejektilinjan viimeisen lajittimen rejekti käännettiin palaamaan jälkilajittelun sijaan rejektilinjan kaariseulalle, vaikutti koko hiomon kapasiteettiin ja rejektilinjan massan laatuun. Koeajojen tuloksena havaittiin, että kytkentämuutolla pystyttiin nostamaan koko hiomon kapasiteettia ja rejektilinjan akseptin laatu parani.

PCC-täyteaineen vaikutus hienopaperin lujuuskäyttäytymiseen nopeassa vetokuormituksessa

Raaka-ainekustannusten minimoimiseksi hienopaperin valmistajat pyrkivät jatkuvasti vähentämään massan havuselluosuutta ja lisäämään paperin täyteainepitoisuutta. PCC:n käyttö hienopaperin täyteaineena on kasvanut viimeisen kymmenen vuoden aikana voimakkaasti. PCC:n etuna on sen joustava valmistusprosessi, jonka olosuhteita säätelemällä voidaan valmistaa hyvin erilaisia tuotteita. PCC:n ominaisuudet, kuten partikkelikoko ja kidemuoto vaikuttavat merkittävästi paperin reologisiin ominaisuuksiin. Täyteaineen vaikutus paperin lujuusominaisuuksiin riippuu oleellisesti siitä, miten täyteaine sijoittuu kuituverkostossa. Lisäksi paperikoneen ajettavuuden turvaamiseksi täyteaineretention tulisi olla riittävän korkealla tasolla. Täyteaineen retentoituminen on hyvin riippuvainen kuitumateriaalin ja täyteaineen ominaisuuksista. Täyteainepitoisuuden lisääminen ja havusellun vähentäminen heikentävät hienopaperin reologisia ominaisuuksia ja vaikuttavat negatiivisesti paperikoneen ajettavuuteen. Varsinkin rainan siirto avoimella viennillä puristinosalta kuivatusosalle voi muodostua ajettavuuden kannalta kriittiseksi kohdaksi. Tämän vuoksi on tärkeää tuntea irrotustapahtumaan ja rainan kireyteen vaikuttavat tekijät. Märän rainan lujuuskäyttäytymistä voidaan tutkia esim. laboratorioarkeista tehtävillä vetolujuus- ja jännitysrelaksaatiomittauksilla. Työn kokeellisessa osassa tutkittiin kahden erityyppisen PCC-täyteaineen vaikutusta hienopaperin vetolujuus- ja relaksaatiokäyttäytymiseen nopeassa vetokuormituksessa. Täyteainepitoisuuden kasvaessa sekä märän että kuivan paperin vetolujuus ja relaksaatiokireys heikkenivät voimakkaasti. Täyteaine myös vähensi havuselluosuuden vaikutusta näihin ominaisuuksiin. PCC:n ominaisuuksilla voitiin hieman vaikuttaa hienopaperin reologisiin ominaisuuksiin, joskin niiden kannalta edullisempi täyteaine antoi paperille huonommat optiset ominaisuudet. Kuiva-ainepitoisuuden kasvaessa paperin vetolujuus ja relaksaatiokireys paranivat eksponentiaalisesti. Tämän perusteella täyteainetyypin vaikutus vedenpoistoon on paperin reologisten ominaisuuksien kannalta tärkeä tekijä.

Brightness of multilayer boards

A good appearance of a package enhances the sale of the product. The packing gives information about the content and instructions for the usage. In this master’s thesis, the optical properties of multilayer packaging board is studied. Especially means of increasing brightness of the multilayer board are evaluated. In the literature part, the effect of different factors on optical properties of a multilayer board are evaluated with the help of light scattering and absorption coefficients. The Kubelka-Munk theory can be used also in modelling brightness of the multilayer board. A large variety of different process factors, chemical aids and machine variables affect optical properties of board. In the experimental part, different methods to increase brightness of a 3-layer board were evaluated. It was discovered that brightness variation of broke (30 % share of the center layer pulp) have only minor influence on brightness of the board. The brightness variation must be high, roughly 9 % in order to alter brightness of the board by 1 %. Higher brightness can be achieved by bleaching the pulp, which holds the largest share of the center layer pulp. Here, 2,6 % increase in brightness of the pulp (60 % share of the center layer pulp) increased brightness of the board by 1 %. In a trial run at a board machine, there was no indication of decreased bulk of the board due to extended bleaching of the pulp. With pulp dyeing appearance and optical properties of a multilayer board can be influenced. By using bluish dyes the natural yellowness of pulps can be decreased and impression of whiteness is then increased. Brightness may deteriorate though, because of increasing light absorption of the dyed pulps. When the yellowness comes from the center layer pulp, the dye should be introduced there. Then the brightness decreasing effect of the dye decreases brightness of the board less. It was noticed that it is more important to maintain brightness of the top layer than brightness of the center layer, because the top layer pulp affects on brightness of the board the most. By introducing fillers into the top layer of a multilayer board it is possible to increase brightness of the board. Fillers with the highest light scattering increased the brightness of the board the most. Increasing light scattering increases brightness and also opacity. Higher opacity in the top layer decreases also the darkening effect of the center layer. Calcinated kaolin and PCC was found to increase the light scattering of the top layer the most at the filler comparison. Introducing fillers into the top layer of multilayer board may decrease bulk and modulus of elasticity of the top layer. This could lead to deteriorated bending stiffness.