Rheology of high solids surface size starches

Tämän diplomityön tarkoituksena oli tutkia pintaliimatärkkelysten reologista käyttäytymistä korkeissa kuiva-ainepitoisuuksissa. Tarve työn suorittamiselle syntyi kun tutkittiin pintaliimausta filminsiirtopuristimella tavallista korkeammissa kuiva-ainepitoisuuksissa, sileän sauvan ollessa applikointilaitteena. Koska applikointi sileällä sauvalla tapahtuu hydrodynaamisten periaatteiden mukaisesti, sen käyttö edellyttää pintaliimojen reologisten ominaisuuksien tarkkaa tuntemusta ja hallintaa.Kiinnostuksen kohteena olevat ominaisuudet olivat tärkkelysten kuiva-ainepitoisuuden (8 – 30 %) vaikutus viskositeettiin eri lämpötiloissa (20, 30, 40 ja 50 ºC), leikkausnopeus alueella 1 s-1 - 700 000 s-1. Myös tärkkelysten myötörajat määritettiin tutkimuksessa. Viskositeetti eri leikkausnopeusalueilla mitattiin seuraavilla laitteilla: Bohlin VOR (matalat leikkausnopeudet ja myötöraja) ja Hercules HiShear (keskitason leikkausnopeudet) reometrit sekä Eklund kapillaariviskometri (korkeat leikkausno-peudet). Analysoidut tärkkelykset olivat kaksi anionista matalaviskoottista peruna (tärkkelys A) ja ohra (tärkkelys C) tärkkelystä, sekä yksi kationinen korkeaviskoottinen peruna tärkkelys (tärkkelys B). Tutkittujen tärkkelysten Brookfield viskositeetit (100 rpm) olivat (10 % liuos, 60 °C:ssa) tärkkelys A ja C: 25 ± 5 mPas ja tärkkelys B: 100 ± 20 mPas.Tärkkelysliuosten kuiva-ainepitoisuuden noustessa muuttui virtauskäyttäytyminen Newtoniaalisesta leikkausohenevaksi. Leikkausoheneva käyttäytyminen oli voimakkainta tärkkelys B:n kohdalla. Viskositeetti – lämpötila riippuvuus korkeissa leikkausnopeuksissa (esim. 500 000 s-1) oli vähäisempää, mitä oli oletettavissa Brookfield viskositeettiarvojen perusteella. Kaikki tarkkelykset osoittautuivat tiksotrooppisiksi, myös tiksotrooppisuus lisääntyi kuiva-ainepitoisuuden kasvaessa. Tärkkelysten myötörajat osoittautuivat odottamattoman alhaisiksi, kuitenkin varsinkin tärkkelys B:n myötörajat olivat selvästi riippuvaisia lämpötilasta ja kuiva-ainepitoisuudesta. Tutkittujen tärkkelysten virtauskäyttäytyminen oli kirjallisuudessa esitetyn kaltaista. Tärkkelysmolekyylien ketjun pituus oli tärkein tärkkelyksen reologisia ominaisuuksia määrittävä tekijä; mitä matalampi on tärkkelyksen molekyylimassa, sitä matalammat ovat viskositeetti ja myötöraja. Pintaliimauksessa tärkkelysmolekyylien ketjunpituudella on suuri vaikutus ajettavuuteen ja lopputuotteen ominaisuuksiin. Haasteellista pintaliimatärkkelyksen valinnassa on sellaisen yhdistelmän löytäminen, jossa sopivan reologisen käyttäytymisen omaava tärkkelys ja pintaliimatulle paperille tai kartongille asetetut vaatimukset kohtaavat.

The finite-sample size of the BDS test for GARCH standardized residuals

This paper uses a multivariate response surface methodology to analyze the size distortion of the BDS test when applied to standardized residuals of rst-order GARCH processes. The results show that the asymptotic standard normal distribution is an unreliable approximation, even in large samples. On the other hand, a simple log-transformation of the squared standardized residuals seems to correct most of the size problems. Nonethe-less, the estimated response surfaces can provide not only a measure of the size distortion, but also more adequate critical values for the BDS test in small samples.

Nanoparticle reactivity toward dithiothreitol

Hazard determination of nanoparticles (NP) is challenging and should be based on a predictive and pragmatic tier approach. The biological effects of NP appear to be related not only to surface/size but also to their ability to generate free radicals/oxidants. We propose that the measurement of this property by acellular assays could be helpful for NP toxicity screening. This study investigated the effect of dispersing conditions on the oxidative capacity of a small selection of carbonaceous NP toward dithiothreitol (DTT). Increasing surfactant concentration decreased the DTT reactivity on these studied particles. Afterward, a panel of NP were studied under constant conditions. Classification of the NP panel based on their DTT reactivity was found to be dependent on the metric used (mass or surface) but not on the surfactant type. The DTT assay may be useful for an initial evaluation of the hazardousness of manufactured or unintentionally produced NP. However, the predictive potential of such a test towards biological effects still needs to be evaluated. [Authors]

BimTwin - Two component continuous process hygiene concept

The aim of this study was to examine suitability of BimTwin cleaning concept in card board machine to control microbiological activity and describe microbiological balance of the machine. In a review of literature is examined microbe and spore caused problems in paper industry. Biggest problems are deposits, which decrease runnability and cause quality errors. In this chapter is also introduced most common oxidizing biocides used in paper industry and described ATP assay as a microbiological monitoring method. In an experimental part are included BimTwin mill trial results, chemical condition monitoring methods and microbiological balance in a card board machine. In a second part are examined possibilities to effect hygiene of card board by chemical treatment of the surface size and coating. Result showed that BimTwin concept is suitable for card board machine as a cleaning concept, when chemical dosing is fitted right. For proper dosing and secure tolerable hygiene level, chemical and microbiological monitoring is significant. Determining of the microbiological balance would have need more sampling. According to acquired results, broke turned out to be the biggest microbe source. Sizing and coating experiments showed that it is possible to improve hygiene of card board by chemically treated surface size and coating color.

Kartongin reunaimeytymän hallittavuus

Kuppikartongin yksi tärkeimmistä ominaisuuksista on reunaimeytymän vastustuskyky, joka tulee olla riittävällä tasolla laadun takaamiseksi. Koska yksinkertainen juomakuppi on bulkki¬tuote, ei sen raakareunaa kannata taloudellisuuden vuoksi suojata tätä varten kehitellyillä menetelmillä vaan itse kartongin tulee vastustaa nesteitä riittävässä määrin. Tämän diplomityön tarkoituksena oli selvittää hydrofobointiin käytettävän massaliiman (hartsi) sekä pintaliiman joukkoon annosteltavan lisäaineen välinen optimaalinen suhde parhaan vastustuskyvyn saavuttamiseksi. Lisäksi selvitettiin joidenkin liimapuristimen ajo-olosuhteiden vaikutusta pintaliiman pick-upiin sekä koneen pH-tason oikeellisuus. Jauhatuksen vaikutusta tutkittiin lähinnä historiatietojen avulla. Tutkimus koostui viidestä tehdasmittakaavaisesta koeajosta, joiden avulla selvitettiin muuttujien vaikutus sisäisellä reunaimeytymän määritysmenetelmällä sekä määrittä¬mällä koepisteistä kulloinkin mielenkiinnon kohteena olleet kemikaalipitoisuudet. Viimeisen koeajon koepisteet jalostettiin lisäksi valmiiksi kupeiksi. Käytetty reunaimeytymän määritysmenetelmä osoittautui virhealttiiksi eivätkä raakakartongista tehtyjen määritysten tulokset korreloineet kovinkaan voimakkaasti PE-päällystettyjen näytteiden kanssa. Menetelmän kehitystä on viety eteenpäin tämän työn rinnalla ja työ jatkuu edelleen. Lisäksi kartongin hartsipitoisuusmääritysten tuloksista paljastui ristiriitaisuuksia, joiden vuoksi menetelmää uusittiin voimakkaasti. Reunaimeytymän vastustuksen riittävyydeksi koneella käytettävien massaliima-annosten tulee olla vähintään valitulla nollatasolla kaikissa kerroksissa ja pintaliiman lisäaine tulee pitää käytössä. Mikäli lisäaine jätetään pois käytöstä, tulee massaliima-annokset olla hyvin korkeita, eikä tämäkään takaa täysin reunaimeytymätöntä lopputuotetta. Lisäaineen ollessa käytössä ei suuremmalla massaliima-annoksella ole puolestaan merkittävää vaikutusta. Konetta ajetaan nykyisin hyvin alhaisella pH-tasolla, mutta tason nostaminen aiheuttaa selvän liimauksen heikkenemisen. Liimapuristimelle tulevan radan kosteudella ja pintaliiman kuiva-aineella ei näyttäisi olevan vaikutusta kartongin reunaimeytymän vastustuskykyyn. Myöskään taustakerroksen koivun jauhatusasteella ei ole merkitystä alueella, jolla koneella operoidaan. CTMP-massan jauhatuksen tulee sen sijaan olla riittävä, jotta keskikerrokseen ei synny yksittäisiä, pitkiä imeytymiä.

Armor coats, inverse grading, and streambed scour in selected streams of Southern Ontario and Western New York /

Surface size analyses of Twenty and Sixteen Mile Creeks, the Grand and Genesee Rivers and Cazenovia Creek show three distinct types of bed-surface sediment: 1) a "continuous" armor coat which has a mean size of -6.5 phi and coarser, 2) a "discontinuous" armor coat which has a mean size of approximately -6.0 phi and 3) a bed with no armor coat which has a mean surface size of -5.0 phi and finer. The continuous armor coat completely covers and protects the subsurface from the flow. The discontinuous armor coat is composed of intermittently-spaced surface clasts, which provide the subsurface with only limited protection from the flow. The bed with no armor coat allows complete exposure of the subsurface to the flow. The subsurface beneath the continuous armor coats of Twenty and Sixteen Mile Creeks is possibly modified by a "vertical winnowing" process when the armor coat is p«natrat«d. This process results in a welld «v«loped inversely graded sediment sequence.vertical winnowing is reduced beneath the discontinuous armor coats of the Grand and Genesee Rivers. The reduction of vertical winnowing results in a more poorly-developed inverse grading than that found in Twenty and sixteen Mile Creeks. The streambed of Cazenovia Creek normally is not armored resulting in a homogeneous subsurface which shows no modification by vertical winnowing. This streambed forms during waning or moderate flows, suggesting it does not represent the maximum competence of the stream. Each population of grains in the subsurface layers of Twenty and sixteen Mile Creeks has been modified by vertical winnowing and does not represent a mode of transport. Each population in the subsurface layers beneath a discontinuous armor coat may partially reflect a transport mode. These layers are still inversely graded suggesting that each population is affected to some degree by vertical winnowing. The populations for sediment beneath a surface which is not armored are probably indicative of transport modes because such sediment has not been modified by vertical winnowing. Bed photographs taken in each of the five streams before and after the 1982-83 snow-melt show that the probability of movement for the surface clasts is a function of grain size. The greatest probability of of clast movement and scour depth of this study were recorded on Cazenovia Creek in areas where no armor coat is present. The scour depth in the armored beds of Twenty and Sixteen Mile Creeks is related to the probability of movement for a given mean surface size.

Finite size effects on the electrical properties of sol–gel synthesized CoFe2O4 powders: deviation from Maxwell–Wagner theory and evidence of surface polarization effects

Fine particles of cobalt ferrite were synthesized by the sol–gel method. Subsequent heat treatment at different temperatures yielded cobalt ferrites having different grain sizes. X-ray diffraction studies were carried out to elucidate the structure of all the samples. Dielectric permittivity and ac conductivity of all the samples were evaluated as a function of frequency, temperature and grain size. The variation of permittivity and ac conductivity with frequency reveals that the dispersion is due to Maxwell–Wagner type interfacial polarization in general, with a noted variation from the expected behaviour for the cold synthesized samples. High permittivity and conductivity for small grains were explained on the basis of the correlated barrier-hopping model

Size-dependent surface plasmon resonance in silver silica nanocomposites

Silver silica nanocomposites were obtained by the sol–gel technique using tetraethyl orthosilicate (TEOS) and silver nitrate (AgNO3) as precursors. The silver nitrate concentration was varied for obtaining composites with different nanoparticle sizes. The structural and microstructural properties were determined by x-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). X-ray photoelectron spectroscopic (XPS) studies were done for determining the chemical states of silver in the silica matrix. For the lowest AgNO3 concentration, monodispersed and spherical Ag crystallites, with an average diameter of 5 nm, were obtained. Grain growth and an increase in size distribution was observed for higher concentrations. The occurrence of surface plasmon resonance (SPR) bands and their evolution in the size range 5–10 nm is studied. For decreasing nanoparticle size, a redshift and broadening of the plasmon-related absorption peak was observed. The observed redshift and broadening of the SPR band was explained using modified Mie scattering theory

Does reactive surface area depend on grain size? Results from pH 3, 25 circle C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 mu m were dissolved in pH 3, HCl at 25 degrees C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 X 10(-10) mol(feldspar) m(-2) s(-1), rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 X 10(-10) mol(feldspar) m(-2) s(-1) and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol(feldspar) g(-1) s(-1). For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 X 10(-12) mol(biotite) m(-2) s(-1), rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 X 10(-12) mol(biotite) m(-2) s(-1), rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 x 10(-12) mol(biotite) m(-2) s(-1) and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 X 10(-12) mol(biotite) g(-1) s(-1). For all normalising terms rates varied significantly (p <= 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over wich they would change significantly. (c) 2006 Elsevier Inc. All rights reserved.

Carbon fractions associated with silt-size particles in surface and subsurface soil horizons

Information on the distribution and behavior of C fractions in soil particle sizes is crucial for understanding C dynamics in soil. At present little is known about the behavior of the C associated with silt-size particles. We quantified the concentrations, distribution, and enrichment of total C (TC), readily oxidizable C (ROC), hotwater- extractable C (HWC), and cold-water-extractable C (CWC) fractions in coarse (63–20-mm), medium (20–6.3-mm), and fine (6.3–2-mm) silt-size subfractions and in coarse (2000–250 mm) and fine (250–63 mm) sand and clay (<2-mm) soil fractions isolated from bulk soil (<2 mm), and 2- to 4-mm aggregate-size fraction of surface (0–25 cm) and subsurface (25–55 cm) soils under different land uses. All measured C fractions varied significantly across all soil particle-size fractions. The highest C concentrations were associated with the <20-mm soil fractions and peaked in the medium (20–6.3-mm) and fine (6.3–2-mm) silt subfractions in most treatments. Carbon enrichment ratios (ERC) revealed the dual behavior of the C fractions associated with the medium silt-size fraction, demonstrating the simultaneous enrichment of TC and ROC, and the depletion of HWC and CWC fractions. The medium silt (20–6.3-mm) subfraction was identified in this study as a zone where the associated C fractions exhibit transitory qualities. Our results show that investigating subfractions within the silt-size particle fraction provides better understanding of the behavior of C fractions in this soil fraction.

Can carbon surface oxidation shift the pore size distribution curve calculated from Ar, N(2) and CO(2) adsorption isotherms? Simulation results for a realistic carbon model

Using the virtual porous carbon model proposed by Harris et al, we study the effect of carbon surface oxidation on the pore size distribution (PSD) curve determined from simulated Ar, N(2) and CO(2) isotherms. It is assumed that surface oxidation is not destructive for the carbon skeleton, and that all pores are accessible for studied molecules (i.e., only the effect of the change of surface chemical composition is studied). The results obtained show two important things, i.e., oxidation of the carbon surface very slightly changes the absolute porosity (calculated from the geometric method of Bhattacharya and Gubbins (BG)); however, PSD curves calculated from simulated isotherms are to a greater or lesser extent affected by the presence of surface oxides. The most reliable results are obtained from Ar adsorption data. Not only is adsorption of this adsorbate practically independent from the presence of surface oxides, but, more importantly, for this molecule one can apply the slit-like model of pores as the first approach to recover the average pore diameter of a real carbon structure. For nitrogen, the effect of carbon surface chemical composition is observed due to the quadrupole moment of this molecule, and this effect shifts the PSD curves compared to Ar. The largest differences are seen for CO2, and it is clearly demonstrated that the PSD curves obtained from adsorption isotherms of this molecule contain artificial peaks and the average pore diameter is strongly influenced by the presence of electrostatic adsorbate-adsorbate as well as adsorbate-adsorbent interactions.

Synergetic effect of carbon nanopore size and surface oxidation on CO2 capture from CO2/CH4 mixtures

We have studied the synergetic effect of confinement (carbon nanopore size) and surface chemistry (the number of carbonyl groups) on CO2 capture from its mixtures with CH4 at typical operating conditions for industrial adsorptive separation (298 K and compressed CO2CH4 mixtures). Although both confinement and surface oxidation have an impact on the efficiency of CO2/CH4 adsorptive separation at thermodynamics equilibrium, we show that surface functionalization is the most important factor in designing an efficient adsorbent for CO2 capture. Systematic Monte Carlo simulations revealed that adsorption of CH4 either pure or mixed with CO2 on oxidized nanoporous carbons is only slightly increased by the presence of functional groups (surface dipoles). In contrast, adsorption of CO2 is very sensitive to the number of carbonyl groups, which can be examined by a strong electric quadrupolar moment of CO2. Interestingly, the adsorbed amount of CH4 is strongly affected by the presence of the co-adsorbed CO2. In contrast, the CO2 uptake does not depend on the molar ratio of CH4 in the bulk mixture. The optimal carbonaceous porous adsorbent used for CO2 capture near ambient conditions should consist of narrow carbon nanopores with oxidized pore walls. Furthermore, the equilibrium separation factor was the greatest for CO2/CH4 mixtures with a low CO2 concentration. The maximum equilibrium separation factor of CO2 over CH4 of ∼18–20 is theoretically predicted for strongly oxidized nanoporous carbons. Our findings call for a review of the standard uncharged model of carbonaceous materials used for the modeling of the adsorption separation processes of gas mixtures containing CO2 (and other molecules with strong electric quadrupolar moment or dipole moment).

Diel surface temperature range scales with lake size

Ecological and biogeochemical processes in lakes are strongly dependent upon water temperature. Long-term surface warming of many lakes is unequivocal, but little is known about the comparative magnitude of temperature variation at diel timescales, due to a lack of appropriately resolved data. Here we quantify the pattern and magnitude of diel temperature variability of surface waters using high-frequency data from 100 lakes. We show that the near-surface diel temperature range can be substantial in summer relative to long-term change and, for lakes smaller than 3 km2, increases sharply and predictably with decreasing lake area. Most small lakes included in this study experience average summer diel ranges in their near-surface temperatures of between 4 and 7°C. Large diel temperature fluctuations in the majority of lakes undoubtedly influence their structure, function and role in biogeochemical cycles, but the full implications remain largely unexplored.