Estudo da influência dos íons K+, Mg2+, SO4(2-) e CO3(2-) na cristalização biomimética de fosfato de cálcio amorfo (ACP) e conversão a fosfato octacálcico (OCP)

The crystallization of hydroxyapatite (HA) in aqueous solution can be described by the mechanism ACP -> OCP -> HA. In this work, it was studied the influence of K+, Mg2+, SO4(2-) and CO3(2-) ions in the formation of ACP and in its conversion to OCP, using biomimetic coatings on metallic substrates of commercially pure titanium (Ti c.p.). The results showed that Mg2+ and CO3(2-) ions favored both the formation of ACP and its conversion to OCP. Differently, K+ and SO4(2-) ions did not influence the formation of ACP and, consequently, interfered in the conversion to OCP.

Preparação, caracterização e propriedades de filmes poliméricos com potencial aplicação no recobrimento de sementes

Films of sodium carboxymethyl cellulose, sodium alginate and their mixture were evaluated in terms of interactions between the polymers, morphology, water absorption and application as seed coatings. FTIR analysis suggested that only hydrophobic interactions occurred between the polymers. The coating of bean seeds was confirmed by microscopy, indicating the formation of dense and homogeneous films with 7 μm thickness. The obtained films did not affect the germination capacity of the seeds. In summary, the characteristics and properties of the films formed and the water absorption capacity, indicate that these systems are viable for use in seed coating processes.

Fosfatos de cálcio de interesse biológico: importância como biomateriais, propriedades e métodos de obtenção de recobrimentos

For decades the Hydroxyapatite (HA) was only bioceramic of calcium phosphate system used for bone replacement and regeneration, due to its similarity to the mineral phase of bones and teeth. Because its slow degradation, other calcium phosphate classified as biodegradable started to awaken interest, such as: amorphous calcium phosphate (ACP), octacalcium phosphate (OCP) and tricalcium phosphate (TCP). This work presents the evolution of the use of other calcium phosphates due to their better solubility than the HA, comparing their main physical-chemical and biological properties. Are also presented the main methods used to obtain bioceramic coatings on metal and polymer surfaces.

Atividade eletrocatalítica de sistemas biomiméticos da enzima catalase

In this work, we describe the immobilization of the dinuclear compound [Cu2(apyhist)2Cl2](ClO4)2 (1) and its derived cations complexes, obtained in water solution or by deprotonation of the imidazolate moiety in the ligand leading to a cyclic tetranuclear species, in the Nafion® membrane on glass carbon electrode surface. After that, we studied the influence of the equilibrium in the electrocatalytic activity towards the reduction of H2O2 in the development of an amperometric sensor for the analytical determination of hydrogen peroxide. This strategy proved successful, and the electrochemical behaviour of the all complexes formed within the Nafion® coatings was characterized. We also provide evidence that its related cyclic tetranuclear imidazolate-bridged complex acts as a catalysts for the intramolecular, two-electron reduction of H2O2.

Desenvolvimento e uso do compósito de Nb2O5|Cu como revestimento aplicado por aspersão térmica sobre o aço AISI 1020 para proteção contra a corrosão pelo solo em estruturas enterradas

An Nb2O|Cu corrosion-resistant coating was developed and applied onto AISI 1020 steel substrate by Powder Flame Spray. A galvanostatic electrochemical technique was employed, with and without ohmic drop, in four different soils (two corrosively aggressive and two less aggressive). Behavior of coatings in different soils was compared using a cathodic hydrogen reduction reaction (equilibrium potential, overvoltage and exchange current density) focusing on the effect of ohmic drop. Results allow recommendation of Nb2O5|Cu composite for use in buried structure protection.

Adhesivos tipo poliuretano obtenidos a partir de aceite de ricino y almidón químicamente modificados

This study reports the preparation of polyurethane adhesives using polyols obtained from castor oil modified by a transesterification reaction with pentaerythritol and starch modified by glycosylation. The physical properties of the polyols such as hydroxyl value were determined and the infrared spectroscopic analysis of the polyols reported. The effect of varying the hydroxyl value in the polyols on physical properties of polyurethane coatings on wood and steel panels was determined. The characterization of polyurethane coatings carried out by IR spectroscopic analysis, scratch hardness resistance, impact resistance, lap shear strength, T-peel strength measurements, solvent resistance and chemical resistant determination were reported.

Pinnoiteteollisuudessa syntyvien maalijätteiden hyötykäyttö ja uudet liiketoimintamahdollisuudet

Tämän diplomityön tavoite on kartoittaa maalien ja lakkojen valmistuksessa syntyvien sivuvirtojen hyötykäyttöä ja hyötykäyttöpotentiaalia nykyisellään. Työn tarkoitus on toimia esiselvityksenä pinnoiteteollisuuden sivuvirtojen hyötykäyttöön liittyvien liiketoimintamahdollisuuksien syvemmälle analyysille. Teollisuuden sivuvirtoihin liittyvää tietoa kerätään tilastoista ja olemassa olevista raporteista sekä haastattelemalla teollisuus- ja palveluyritysten edustajia sekä alan asiantuntijoita. Sivuvirtojen teknisten hyötykäyttömahdollisuuksien ja liiketoiminnallisten mahdollisuuksien tarkastelua varten järjestetään työpajoja asiantuntijoille Apila Group Oy Ab:n asiantuntijaverkostossa. Neljässä haastatellussa tuotantolaitoksissa syntyi vuonna 2008 yhteensä 6 662 tonnia kiinteää jätettä ja lietteitä. 68 % näistä sivuvirroista hyötykäytettiin energiana tai polttoaineen valmistuksessa. Materiaalina sivuvirtoja hyötykäytettiin 16 % sivuvirroista, pääasiassa pahvia, paperia, metalleja sekä tynnyreitä ja kontteja. Myös merkittävä osa liuottimista otettiin talteen uudelleenhyödyntämistä varten. Tässä diplomityössä hyötykäyttömahdollisuuksien tarkempaa tarkastelua varten valittiin tavanomaisiksi jätteiksi luokiteltuja maalisivuvirtoja, joita haastatelluissa tuotantolaitoksissa syntyi noin 1 500 tonnia. Maalisivuvirtojen tärkeimmät materiaaliominaisuudet liittyvät niiden sisältämiin täyte- ja sideaineisiin, jotka muodostavat merkittävän osan maalien koostumuksesta. Selvityksen mukaan nämä ominaisuudet voidaan ottaa hyötykäyttöön erilaisissa yhdistelmämateriaaleissa, esimerkiksi ekstruusiopuristetuissa tai ahtopuristetuissa muovikuitukomposiiteissa. Komposiittien raaka-aineena käytetään jo erilaisia sivuvirtoja ja lisäksi erilaisten komposiittien markkinoiden ennustetaan kasvavan. Tämä voi tarjota mahdollisuuksia uusille palvelu-, t&k- tai tuotteistusliiketoiminnoille. Kuivilla maalijätteillä on myös hyvä lämpöarvo, jolloin energiahyötykäytön ja palamisjäännöksen materiaalihyötykäytön yhdistäminen mm. keramiikka- tai sementtiteollisuudessa voi tarjota mahdollisuuksia uusille liiketoiminnoille.

Influence of plasma modification on surface properties and offset printability of coated paper

The properties of the paper surface play a crucial role in ensuring suitable quality and runnability in various converting and finishing operations, such as printing. Plasma surface modification makes it possible to modify the surface chemistry of paper without altering the bulk material properties. This also makes it possible to investigate the role of the surface chemistry alone on printability without influencing the porous structure of the pigment-coated paper. Since the porous structure of a pigment coating controls both ink setting and optical properties, surface chemical changes created by a plasma modification have a potential to decouple these two effects and to permit a better optimization of them both. The aim of this work was to understand the effects of plasma surface modification on paper properties, and how it influences printability in the sheet-fed offset process. The objective was to broaden the fundamental understanding of the role of surface chemistry on offset printing. The effects of changing the hydrophilicity/ hydrophobicity and the surface chemical composition by plasma activation and plasma coatings on the properties of coated paper and on ink-paper interactions as well as on sheet-fed offset print quality were investigated. In addition, the durability of the plasma surface modification was studied. Nowadays, a typical sheet-fed offset press also contains units for surface finishing, for example UVvarnishing. The role of the surface chemistry on the UV-varnish absorption into highly permeable and porous pigment-coated paper was also investigated. With plasma activation it was possible to increase the surface energy and hydrophilicity of paper. Both polar and dispersion interactions were found to increase, although the change was greater in the polar interactions due to induced oxygen molecular groups. The results indicated that plasma activation takes place particularly in high molecular weight components such as the dispersion chemicals used to stabilize the pigment and latex particles. Surface composition, such as pigment and binder type, was found to influence the response to the plasma activation. The general trend was that pilot-scale treatment modified the surface chemistry without altering the physical coating structure, whereas excessive laboratory-scale treatment increased the surface roughness and reduced the surface strength, which led to micro-picking in printing. It was shown that pilot-scale plasma activation in combination with appropriate ink oils makes it possible to adjust the ink-setting rate. The ink-setting rate decreased with linseed-oil-based inks, probably due to increased acid-base interactions between the polar groups in the oil and the plasma-treated paper surface. With mineral-oil-based inks, the ink setting accelerated due to plasma activation. Hydrophobic plasma coatings were able to reduce or even prevent the absorption of dampening water into pigmentcoated paper, even when the dampening water was applied under the influence of nip pressure. A uniform hydrophobic plasma coating with sufficient chemical affinity with ink gave an improved print quality in terms of higher print density and lower print mottle. It was also shown that a fluorocarbon plasma coating reduced the free wetting of the UV-varnish into the highly permeable and porous pigment coating. However, when the UV-varnish was applied under the influence of nip pressure, which leads to forced wetting, the role of the surface chemical composition seems to be much less. A decay in surface energy and wettability occurred during the first weeks of storage after plasma activation, after which it leveled off. However, the oxygen/carbon elemental ratio did not decrease as a function of time, indicating that ageing could be caused by a re-orientation of polar groups or by a contamination of the surface. The plasma coatings appeared to be more stable when the hydrophobicity was higher, probably due to fewer interactions with oxygen and water vapor in the air.

Polymer surface modification by atomic layer deposition

Current industrial atomic layer deposition (ALD) processes are almost wholly confined to glass or silicon substrates. For many industrial applications, deposition on polymer substrates will be necessary. Current deposition processes are also typically carried out at temperatures which are too high for polymers. If deposition temperatures in ALD can be reduced to the level applicable for polymers, it will open new interesting areas and applications for polymeric materials. The properties of polymers can be improved for example by coatings with functional and protective properties. Although the ALD has shown its capability to operate at low temperatures suitable for polymer substrates, there are other issues related to process efficiency and characteristics of different polymers where new knowledge will assist in developing industrially conceivable ALD processes. Lower deposition temperature in ALD generally means longer process times to facilitate the self limiting film growth mode characteristic to ALD. To improve process efficiency more reactive precursors are introduced into the process. For example in ALD oxide processes these can be more reactive oxidizers, such as ozone and oxygen radicals, to substitute the more conventionally used water. Although replacing water in the low temperature ALD with ozone or plasma generated oxygen radicals will enable the process times to be shortened, they may have unwanted effects both on the film growth and structure, and in some cases can form detrimental process conditions for the polymer substrate. Plasma assistance is a very promising approach to improve the process efficiency. The actual design and placement of the plasma source will have an effect on film growth characteristics and film structure that may retard the process efficiency development. Due to the fact that the lifetime of the radicals is limited, it requires the placement of the plasma source near to the film growth region. Conversely this subjects the substrate to exposure byother plasma species and electromagnetic radiation which sets requirements for plasma conditions optimization. In this thesis ALD has been used to modify, activate and functionalize the polymer surfaces for further improvement of polymer performance subject to application. The issues in ALD on polymers, both in thermal and plasma-assisted ALD will be further discussed.

Potkurilaitteen ohjausputken laserpinnoitus

Laserpinnoitus on additiivinen prosessi, jossa lasertehon avulla sulatetaan pinnoitusainetta pinnoitettavan kappaleen pintaan. Laserpinnoituksella on mahdollista aikaansaada tiivis sekä kova, kulutusta ja korroosiota kestävä pinnoite kappaleen pintaan. Tässä työssä kohteena oli potkurilaitteen ohjausputken laserpinnoitus. Kyseisessä kohteessa pinnoitteelta vaaditaan hyvää korroosion- ja kulumisen kestoa. Työn tavoitteena oli lisätä tietoisuutta laserpinnoitusprosessista ja siinä vaikuttavista tekijöistä. Myös materiaaliominaisuuksien vaikutuksia sekä pinnoitus- että pinnoitettavien aineiden osalta selvitettiin. Työhön sisältyi myös kokeellinen osuus, jossa tavoitteena oli löytää kustannustehokkain pinnoiteaine tutkittuun kohteeseen. Kokeissa ohjausputki- sekä levyaihioon tehtiin koepinnoituksia. Kokeiden ja edelleen materiaalitutkimuksien avulla tutkittiin neljää eri pinnoitusainetta, jotka olivat Stellitti 21, Inconel 625, AISI 316L ja AISI 431. Kovuus- ja taivutuskokeiden perusteella kyseisistä aineista vain Stelliitti 21 täytti ohjausputken pinnoitteelle asetetut vaatimukset. Näin ollen Stelliitti 21 valikoitui kustannustehokkaimmaksi pinnoitusaineeksi ohjausputkien laserpinnoitukseen.

Elektrolyyttinen nanopinnoitus

Diplomityö on osa Savonia-amk:n hallinnoimaa ENC- pinnoitushanketta, jossa tutkitaan uuden teknologian elektrolyyttisiä kromi (III) -nanopinnoitteita. Tavoitteena oli selvittää uudella menetelmällä saavutettavat parannukset pinnoitteiden mekaanisiin ominaisuuksiin. Työ toteutettiin rakentamalla pinnoitustutkimuksen toimintaympäristö osaksi Savo-nia-amk:n materiaalitekniikan laboratorioita sekä tutkimalla eri koe- ja sovelluspinnoitteiden mekaanisia ominaisuuksia eri pinnoitusparametreilla. Työssä tutkittiin, miten nanopartikkelit sekä erilaiset pinnoitusparametrit vaikuttavat kromipinnoitteiden rakenteeseen sekä mekaaniseen suorituskykyyn.

Liquid transportation and distribution during (re)wetting : impact on coated papers in printing

In many industrial applications, such as the printing and coatings industry, wetting of porous materials by liquids includes not only imbibition and permeation into the bulk but also surface spreading and evaporation. By understanding these phenomena, valuable information can be obtained for improved process control, runnability and printability, in which liquid penetration and subsequent drying play important quality and economic roles. Knowledge of the position of the wetting front and the distribution/degree of pore filling within the structure is crucial in describing the transport phenomena involved. Although exemplifying paper as a porous medium in this work, the generalisation to dynamic liquid transfer onto a surface, including permeation and imbibition into porous media, is of importance to many industrial and naturally occurring environmental processes. This thesis explains the phenomena in the field of heatset web offset printing but the content and the analyses are applicable in many other printing methods and also other technologies where water/moisture monitoring is crucial in order to have a stable process and achieve high quality end products. The use of near-infrared technology to study the water and moisture response of porous pigmented structures is presented. The use of sensitive surface chemical and structural analysis, as well as the internal structure investigation of a porous structure, to inspect liquid wetting and distribution, complements the information obtained by spectroscopic techniques. Strong emphasis has been put on the scale of measurement, to filter irrelevant information and to understand the relationship between interactions involved. The near-infrared spectroscopic technique, presented here, samples directly the changes in signal absorbance and its variation in the process at multiple locations in a print production line. The in-line non-contact measurements are facilitated by using several diffuse reflectance probes, giving the absolute water/moisture content from a defined position in the dynamic process in real-time. The nearinfrared measurement data illustrate the changes in moisture content as the paper is passing through the printing nips and dryer, respectively, and the analysis of the mechanisms involved highlight the roles of the contacting surfaces and the relative liquid carrier properties of both non-image and printed image areas. The thesis includes laboratory studies on wetting of porous media in the form of coated paper and compressed pigment tablets by mono-, dual-, and multi-component liquids, and paper water/moisture content analysis in both offline and online conditions, thus also enabling direct sampling of temporal water/moisture profiles from multiple locations. One main focus in this thesis was to establish a measurement system which is able to monitor rapid changes in moisture content of paper. The study suggests that near-infrared diffuse reflectance spectroscopy can be used as a moisture sensitive system and to provide accurate online qualitative indicators, but, also, when accurately calibrated, can provide quantification of water/moisture levels, its distribution and dynamic liquid transfer. Due to the high sensitivity, samples can be measured with excellent reproducibility and good signal to noise ratio. Another focus of this thesis was on the evolution of the moisture content, i.e. changes in moisture content referred to (re)wetting, and liquid distribution during printing of coated paper. The study confirmed different wetting phases together with the factors affecting each phase both for a single droplet and a liquid film applied on a porous substrate. For a single droplet, initial capillary driven imbibition is followed by equilibrium pore filling and liquid retreat by evaporation. In the case of a liquid film applied on paper, the controlling factors defining the transportation were concluded to be the applied liquid volume in relation to surface roughness, capillarity and permeability of the coating giving the liquid uptake capacity. The printing trials confirmed moisture gradients in the printed sheet depending on process parameters such as speed, fountain solution dosage and drying conditions as well as the printed layout itself. Uneven moisture distribution in the printed sheet was identified to be one of the sources for waving appearance and the magnitude of waving was influenced by the drying conditions.

Rasvankestävät paperit ja kartongit

Rasvankestävyydellä tarkoitetaan sitä, että materiaali hylkii tai kestää rasvaa tietyn ajan läpäisemättä sen pintaa. Rasvankestäviä papereita ja kartonkeja löytyy kaikkialta. Erilaiset ruuanvalmistuspaperit, kuten esimerkiksi leivinpaperi ja voipaperi, ovat rasvankestäviä. Myös pakkauksissa käytetään paljon rasvankestäviä papereita ja kartonkeja. Rasvankestäviltä tuotteilta vaaditaan erilaisia ominaisuuksia riippuen niiden käyttötarkoituksesta. Pakkausmateriaaleilta vaaditaan esimerkiksi lujuutta ja kestävyyttä fyysistä rasitusta, valoa, hajuja ja mikrobeja vastaan. Ruuanvalmistusmateriaaleilta vaaditaan puolestaan lujuutta ja kestävyyttä lämpöä, kosteutta ja fyysistä rasitusta vastaan. Rasvankestäviltä papereilta vaaditaan rasvankestävyyden lisäksi hyvää vetolujuutta, märkälujuutta ja hyviä optisia ominaisuuksia. Neliömassan tulee asettua 20─80 g/m2 välille ja metallipitoisuudet eivät saa olla liian korkeat. Myös tuotteiden kierrätettävyys on nostanut asemaansa viimeaikoina. Tuotteen tuotannon ja itse tuotteen ympäristöystävällisyys ovat todella arvostettuja kuluttajan, tuottajan, Suomen, EU:n ja koko maailman näkökulmista. Jotta tuotteesta saadaan rasvankestävää, vaaditaan siltä erilaisia barrier-ominaisuuksia. Rasvankestävällä paperilla vaaditaan hyviä barrier-ominaisuuksia esimerkiksi rasvan, ilman, veden, vesihöyryn sekä hapen läpäisevyyksissä. Rasvankestäviä papereita ja kartonkeja voidaan valmistaa kemiallisilla ja mekaanisilla tavoilla. Happokäsittely ja fluorokemikaalien lisääminen ovat kemiallisia tapoja, kun taas sellun jauhaminen pitkään matalassa lämpötilassa on mekaaninen tapa valmistaa rasvankestävää paperia. Näiden tapojen lisäksi rasvankestäviä papereita voidaan tehdä erilaisten pinnoitusten avulla. Erilaiset muovit ovat yleisemmin käytettyjä pinnoitemateriaaleja. Esimerkiksi PE- ja PET-päällysteet ovat käytettyjä rasvankestävissä tuotteissa. Viime aikoina on kehitetty paljon erilaisia biomateriaaleja, joista voidaan tehdä rasvankestävä pinnoite. Lipideistä, hydrokolloideista ja erilaisista komposiiteista voidaan luoda uusien tekniikoiden avulla rasvankestäviä pinnoitteita. Rasvankestävyydestä voidaan saada jonkinlainen käsitys WVTR-asteen, Cobb-arvon ja kontaktikulman mittausten avulla. Rasvankestävyyttä voidaan myös mitata erilaisten standarditestien avulla. TAPPI:lla, ISO:lla ja ASTM:llä on useita erilaisia standardeja. Lähes kaikissa rasvankestävyysstandardeissa tuloksen saaminen perustuu visuaaliseen havaintoon, mikä aiheuttaa välillä hankaluuksia tulosten luotettavuuteen, koska tuloksen määrittää ihmissilmä, ja kaikilla testin tekijöillä on erilainen silmä, joka aistii eri tavalla.

Proceedings of the PDM2013 conference, LUT 24.-25.4.2013

The 1st PDM Forum for Finland-Russia Collaboration was held at Lappeenranta University of Technology, Finland, during 25.-26.4.2013. The forum brought together leading academics, practitioners, advisors, engineers, industrial experts, and software vendors from Finland and Russia. The forum can be seen as a new integrating element between Russian and Finnish industries and universities. Over border connections between Russia and Finland may also bring new contacts and ideas to develop and expand businesses. Meeting different universities professors, PhD students, and companies’ agents facilitates the sharing and discussion of current PDM (Product Data Management) issues.

Gelatin as an additive in bio-based barrier films

The main objective of the present study was to verify the approach on starch-gelatin blending for the paperboard coating formulations with enhanced barrier and mechanical properties. Based on that, another objective was to find out, how the approach will function with wood-based polysaccharides (CMC, EHEC and HPC) by analyzing their barrier properties and convertibility. The last objective was to find out, if pigments can be used in the composition of polysaccharide-protein blends without causing any negative effect on stated properties. The whole process chain of the barrier coating development was studied in the research. The methodology applied included pilot-scale coating and converting trials for the evaluation of mechanical properties of obtained coatings, namely their exposure to cracking with the loss of barrier properties. The results obtained indicated that the combination of starch with gelatin, in fact, improves the grease barrier properties and flexibility of starch-based coatings, thereby confirming the offered approach. The similar results were obtained for CMC, exhibited elevated barrier properties and surface coverage, proving that the approach also functions with wood-based polysaccharides. The introduction of equal amounts of talc gave various effects at different gelatin dosages on barrier properties of wood-based polysaccharides. Mainly, the elevation of grease barrier properties was observed. The convertibility of talc-filled coatings was not sufficient.