Formulazioni di blend a base di acido polilattico e biochar per la termoformatura di imballaggi alimentari

In questo studio verranno descritte formulazioni di materiali innovativi, completamente biodegradabili e compostabili, a base di acido polilattico e biochar. Queste formulazioni sono state ideate per applicazioni nel settore degli imballaggi alimentari, in particolare da utilizzare nella produzione di vaschette ortofrutticole nere termoformate come alternativa alle tradizionali vaschette a base di PP e PET. È stato scelto di testare il biochar poiché rappresenta un composto ecocompatibile esattamente come la matrice polimerica utilizzata, alternativo al carbon black di origine fossile utilizzato in queste applicazioni come colorante. Varie formulazioni di PLA contenenti biochar e plasticizzanti sono state preparate con un miscelatore Brabender e trasformate in fogli tramite una pressa a doppio piatto riscaldante. Da questi film sono stati poi realizzati provini per prove di trazione e strappo. Sono state sviluppate inoltre reazioni di funzionalizzazione sul biochar allo scopo di migliorare la sua la compatibilità con la matrice polimerica rendendo la miscela più omogenea.

Viti riassorbibili in acido polilattico per chirurgia del piede: Analisi critica delle proprietà meccaniche e tecnologiche, studio dell'esperienza clinica, e caratterizzazione chimica e meccanica

Recentemente, l'uso di polimeri a base di acido polilattico (PLA) ha subito un fortissimo incremento, soprattutto per la produzione di dispositivi atti alla fissazione di fratture e osteotomie. Lo scopo della prima parte del mio lavoro di tesi, è stato quello di redigere un documento che contenesse informazioni sulle caratteristiche dell'acido poli-L-lattico (PLLA) e del polimero P(L-DL)LA70:30 (70% di PLLA + 30% di PDLLA), entrambi molto diffusi nelle applicazioni biomediche. A tale scopo, è stata fatta un'analisi dello stato dell'arte sulle proprietà chimico-fisiche, tecnologiche (produzione e sterilizzazione) e sui principali meccanismi di degradazione. La seconda parte, invece, è stata dedicata alla stesura di una review sull'evoluzione della biocompatibilità del PLLA utilizzato in ambito ortopedico. A tale scopo, data la grande quantità di studi presenti in letteratura (in vitro, in vivo, trial clinici), non è stato necessario eseguire nessun test per validarne la biocompatibilità. Tuttavia, nonostante trovino già largo impiego nella chirurgia ortopedica, i polimeri in PLA continuano ad essere oggetto di studio, con l'obiettivo di comprenderne al meglio il comportamento e realizzare dispositivi sempre più sicuri ed efficaci per la salute del paziente. E' proprio in questo ambito di ricerca che si inserisce l'attività sperimentale svolta presso lo stabilimento Lima Corporate di Villanova di San Daniele del Friuli (UD). In particolare, l'ultima parte del lavoro di tesi, è stata dedicata alla valutazione degli effetti che il processo di sterilizzazione ad Ossido di Etilene (EtO), genera sulle proprietà chimico-fisiche e meccaniche della vite CALCANEO-STOP in PLLA, stampata ad iniezione e realizzata da Hit Medica (del gruppo Lima Corporate) nello stabilimento di San Marino (RSM). Per la caratterizzazione chimico-fisica del materiale sono state condotte prove di: densitometria, calorimetria a scansione differenziale (DSC), spettrometria FT-IR e viscosimetria. Per la caratterizzazione meccanica dei dispositivi, sono state condotte delle prove a torsione statica.

Nuovi copolimeri triblocco biodegradabili a base di PLA per imballaggi alimentari

Nella presente Tesi si procede alla preparazione e caratterizzazione di nuovi poliesteri alifatici a base di PLLA che offrano garanzie di completa biodegradabilità e presentino caratteristiche chimico/fisiche adeguate ad applicazioni nell’ambito dell’imballaggio alimentare. La modifica chimica del PLLA è stata realizzata per introduzione in catena di segmenti opportunamente sintetizzati che fungono da iniziatori nell’apertura dell’anello di lattide nella ROP. I copolimeri triblocco, poli(lattico)-block-poli(propilene/neopentil glicole succinato) PLLAnP(PS80NS20)m, si differenziano per il diverso rapporto in peso tra i due diversi tipi di blocco, quello hard di PLLA e quello soft di P(PS80NS20). I risultati ottenuti sono di rilevante interesse applicativo: i copolimeri presentano migliorate proprietà meccaniche rispetto al PLLA, una maggiore velocità di biodegradazione, senza che abbia avuto luogo un peggioramento della stabilità termica e delle proprietà barriera, addirittura migliore al gas test O2.

Derivati naturali dell'acido difenolico per la sostituzione del bisfenolo A

La produzione di materie plastiche da fonti rinnovabili è oggi uno dei principali obiettivi della chimica dei polimeri. Anche se i materiali termoplastici da fonte “bio” sono stati già ampiamente studiati, non si può affermare lo stesso per i termoidurenti. Le resine epossidiche sono ampiamente usate come rivestimenti, adesivi e materiali strutturali grazie alle loro eccezionali proprietà meccaniche e alla buona resistenza al calore. Nonostante ciò, la ricerca svolta in questo campo su tali materiali è molto limitata e la loro produzione deriva ancora dalla reazione tra epicloridrina, cancerogena, e bisfenolo A, sospettato di avere effetti sul sistema ormonale. Per questo, la possibilità di trovare un sostituto per il bisfenolo A è un punto cruciale della chimica per dare una risposta eco-sostenibile alla domanda dei consumatori. L’acido difenolo è stato identificato come un buon canditato per la sostituzione del bisfenolo A, grazie alla similarità delle loro strutture. Dal momento che esso deriva dalla reazione tra acido levulinico, derivante da biomassa e fenolo, è possibile considerarlo un reagente di origine bio. Lo scopo di questo lavoro è quello di sostituire il fenolo con composti fenolici di origine naturale come m-cresolo, guaiacolo, catecolo e resorcinolo. Le molecole risultanti saranno confrontate con il bisfenolo A per ciò che concerne la possibilità di formare i rispettivi glicidil eteri tramite reazione con epicloridrina. Questo permetterebbe la formazione di un pre-polimero epossidico proveniente da fonte rinnovabile in un prossimo futuro.

Effect of biochar amendment on the soil-atmosphere exchange of greenhouse gases from an intensive subtropical pasture in northern New South Wales, Australia

We assessed the effect of biochar incorporation into the soil on the soil-atmosphere exchange of the greenhouse gases (GHG) from an intensive subtropical pasture. For this, we measured N2O, CH4 and CO2 emissions with high temporal resolution from April to June 2009 in an existing factorial experiment where cattle feedlot biochar had been applied at 10 t ha-1 in November 2006. Over the whole measurement period, significant emissions of N2O and CO2 were observed, whereas a net uptake of CH4 was measured. N2O emissions were found to be highly episodic with one major emission pulse (up to 502 µg N2O-N m-2 h 1) following heavy rainfall. There was no significant difference in the net flux of GHGs from the biochar amended vs. the control plots. Our results demonstrate that intensively managed subtropical pastures on ferrosols in northern New South Wales of Australia can be a significant source of GHG. Our hypothesis that the application of biochar would lead to a reduction in emissions of GHG from soils was not supported in this field assessment. Additional studies with longer observation periods are needed to clarify the long term effect of biochar amendment on soil microbial processes and the emission of GHGs under field conditions.

Effects of rice husk biochar and sugar-mill by-products on methane consumption from two different soils

Methane (CH4) is an important greenhouse gas with a global warming potential (GWP) 25 times greater than carbon dioxide (CO2) that can be produced or consumed in soils depending on environmental conditions and other factors. Biochar application to soils has been shown to reduce CH4 emissions and to increase CH4 consumption. However, the effects of rice husk biochar (RB) have not been thoroughly investigated. Two 60-day laboratory incubation experiments were conducted to investigate the effects of amending two soil types with RB, raw mill mud (MM) and composted mill mud (CM) on soil CH4 consumption and emissions. Soil cores incubated in 1 L glass jars and gas samples were analysed for CH4 using gas chromatography. Average CH4 consumption rates varied from -0.06 to -0.68 g CH4-C( )/ha/d in sandy loam soil and -0.59 to -1.00 g CH4-C/ha/d in clay soil. Application of RB resulted in CH4 uptake of -0.52 to -0.55 g CH4-C/ha/d in sandy loam and -0.76 to -0.91 g CH4-C/ha/d in clay soil. Addition of MM showed low CH4 emissions or consumption at 60% water-filled pore space (WFPS) in both soils. However, at high water contents (>75% WFPS) the application of MM produced high rates of CH4 emissions which were significantly suppressed when RB was added. Cumulative emissions of the MM treatment produced 108.9 g CH4-C/ha at 75% WFPS and 11 459.3 g CH4-C/ha at 90% WFPS in sandy loam soil over a period of 60 days. RB can increase CH4 uptake under low soil water content (SWC) and decrease CH4 emissions under anaerobic conditions. CM expressed more potential to reduce CH4 emissions than those of MM.

Microporous bamboo biochar for lithium-sulfur batteries

Being simple, inexpensive, scalable and environmentally friendly, microporous biomass biochars have been attracting enthusiastic attention for application in lithium-sulfur (Li-S) batteries. Herein, porous bamboo biochar is activated via a KOH/annealing process that creates a microporous structure, boosts surface area and enhances electronic conductivity. The treated sample is used to encapsulate sulfur to prepare a microporous bamboo carbon-sulfur (BC-S) nanocomposite for use as the cathode for Li-S batteries for the first time. The BC-S nanocomposite with 50 wt.% sulfur content delivers a high initial capacity of 1,295 mA·h/g at a low discharge rate of 160 mA/g and high capacity retention of 550 mA·h/g after 150 cycles at a high discharge rate of 800 mA/g with excellent coulombic efficiency (⩾95%). This suggests that the BC-S nanocomposite could be a promising cathode material for Li-S batteries.

Rice husk biochar and crop residue amendment in subtropical cropping soils: Effect on biomass production, nitrogen use efficiency and greenhouse gas emissions

We investigated the effect of maize residues and rice husk biochar on biomass production, fertiliser nitrogen recovery (FNR) and nitrous oxide (N2O) emissions for three different subtropical cropping soils. Maize residues at two rates (0 and 10 t ha−1) combined with three rates (0, 15 and 30 t ha-1) of rice husk biochar were added to three soil types in a pot trial with maize plants. Soil N2O emissions were monitored with static chambers for 91 days. Isotopic 15N-labelled urea was applied to the treatments without added crop residues to measure the FNR. Crop residue incorporation significantly reduced N uptake in all treatments but did not affect overall FNR. Rice husk biochar amendment had no effect on plant growth and N uptake but significantly reduced N2O and carbon dioxide (CO2) emissions in two of the three soils. The incorporation of crop residues had a contrasting effect on soil N2O emissions depending on the mineral N status of the soil. The study shows that effects of crop residues depend on soil properties at the time of application. Adding crop residues with a high C/N ratio to soil can immobilise N in the soil profile and hence reduce N uptake and/or total biomass production. Crop residue incorporation can either stimulate or reduce N2O emissions depending on the mineral N content of the soil. Crop residues pyrolysed to biochar can potentially stabilise native soil C (negative priming) and reduce N2O emissions from cropping soils thus providing climate change mitigation potential beyond the biochar C storage in soils. Incorporation of crop residues as an approach to recycle organic materials and reduce synthetic N fertiliser use in agricultural production requires a thorough evaluation, both in terms of biomass production and greenhouse gas emissions.

Effect of biochar amendment on yield and photosynthesis of peanut on two types of soils

Abstract Biochar has significant potential to improve crop performance. This study examined the effect of biochar application on the photosynthesis and yield of peanut crop grown on two soil types. The commercial peanut cultivar Middleton was grown on red ferrosol and redoxi-hydrosol (Queensland, Australia) amended with a peanut shell biochar gradient (0, 0.375, 0.750, 1.50, 3.00 and 6.00 %, w/w, equivalent up to 85 t ha−1) in a glasshouse pot experiment. Biomass and pod yield, photosynthesis-[CO2] response parameters, leaf characteristics and soil properties (carbon, nitrogen (N) and nutrients) were quantified. Biochar significantly improved peanut biomass and pod yield up to 2- and 3-folds respectively in red ferrosol and redoxi-hydrosol. A modest (but significant) biochar-induced improvement of the maximumelectron transport rate and saturating photosynthetic rate was observed for red ferrosol. This response was correlated to increased leaf N and accompanied with improved soil available N and biological N fixation. Biochar application also improved the availability of other soil nutrients, which appeared critical in improving peanut performance, especially on infertile redoxihydrosol. Our study suggests that application of peanut shell derived biochar has strong potential to improve peanut yield on red ferrosol and redoxi-hydrosol. Biochar soil amendment can affect leaf N status and photosynthesis, but the effect varied with soil type.

Impact of compost, vermicompost and biochar on soil fertility, maize yield and soil erosion in Northern Vietnam: A three year mesocosm experiment

Compost, vermicompost and biochar amendments are thought to improve soil quality and plant yield. However, little is known about their long-term impact on crop yield and the environment in tropical agro-ecosystems. In this study we investigated the effect of organic amendments (buffalo manure, compost and verrnicompost) and biochar (applied alone or with vermicompost) on plant yield, soil fertility, soil erosion and water dynamics in a degraded Acrisol in Vietnam. Maize growth and yield, as well as weed growth, were examined for three years in terrestrial mesocosms under natural rainfall. Maize yield and growth showed high inter-annual variability depending on the organic amendment. Vermicompost improved maize growth and yield but its effect was rather small and was only significant when water availability was limited (year 2). This suggests that vermicompost could be a promising substrate for improving the resistance of agrosystems to water stress. When the vermicompost biochar mixture was applied, further growth and yield improvements were recorded in some cases. When applied alone, biochar had a positive influence on maize yield and growth, thus confirming its interest for improving long-term soil productivity. All organic amendments reduced water runoff, soil detachment and NH4+ and NO3- transfer to water. These effects were more significant with vermicompost than with buffalo manure and compost, highlighting that the beneficial influence of vermicompost is not limited to its influence on plant yield. In addition, this study showed for the first time that the combination of vermicompost and biochar may not only improve plant productivity but also reduce the negative impact of agriculture on water quality. (C) 2015 Elsevier B.V. All rights reserved.

Estudio del proceso de floracion inducido por el acido giberelico (AG3) en nueve cultivares de quequisque (Xanthosoma spp) en Nicaragua

Se evaluó la floración inducida por tres aplicaciones (semanal y quincenal) de 0,500 y 1000 ppm de acido giberélico (AG3) en los cultivares de quequisque San Ramón, El Tuma, San Antonio, La Rampla, Malaquías,San Lucas, Casitas, Masaya y Apalí. Se utilizó el diseño de bloque completo al azar, con tres bloques, cuatro plantas/bloque y 12 plantas/cultivar. Se evaluó la altura de planta, grosor del pseudotallo, número de hojas y área foliar; momento de floración, número de flores, estructuras relacionadas a la floración, germinación del polen y receptividad del ovario. Previo a la aplicación los cultivares no diferían en desarrollo morfológico. El AG3 retrasó drásticamente el crecimiento de las plantas. Los cultivares iniciaron la floración 88-114 días después de la primera aplicación (ddpa). San Ramón, San Antonio y Malaquías iniciaron la floración 88 ddpa. La Rampla y San Lucas la iniciaron 114 ddpa. La floración duró dos meses. Las plantas produjeron 8 flores promedio. El cultivar San Antonio aplicado con 500 ppm de AG3 semanalmente produjo 102 flores. Aplicaciones quincenales de 1000 ppm indujeron 25 flores en San Ramón y El Tuma, 8 en San Lucas y Casitas. Además se produjeron: brácteas, brácteas múltiples, bráctea hoja de bandera y brácteas cubriendo hoja de bandera. La germinación del polen fue 90-100%. Altas temperaturas al inicio de la floracion afectaron la ántesis y la producción del polen. La receptividad del ovario fue 100%. Este es el primer estudio de inducción de floración en quequisque cuyos resultados son la base de futuros trabajos de mejora genética en el cultivo.

Palm frond biochar production and characterisation

Palm oil has been the world's main source of oil and fats since 2004, producing over 45 million tonnes in 2009. Malaysia alone has over 4·5 million hectares planted with oil palm and, based on common practice, ~300 palm fronds are pruned per hectare per year. This agricultural waste is currently either being used as roughage feed or, more frequently, being left between rows of palm trees to prevent soil erosion, or for nutrient recycling purposes. This paper proposes an alternative use for palm frond as a source of biochar. A traditional method commonly use by gardeners in Malaysia to improve soil fertility was used to produce the biochar. A shallow earth pit was dug in the ground for the carbonisation process. The process is described and the impact of carbonisation on the earth wall is analysed and presented. The process was later re-assessed by using TGA-FTIR. Most of the hemicelluloses had fully disintegrated, but the depolymerisation of the cellulose was still incomplete at the carbonisation temperature. Most of the lignin aromatic structure was still present in the biochar. The carbonisation process was repeated in the laboratory and biochar was characterised by using BET, SEM and FTIR. An adsorption isotherm study was conducted and the experimental data were fitted to the Langmuir model. The model predicted Pb2+ adsorption rates of 83·3 mg/g, Cu2+ 41·4 mg/g, Ni2+ 13·0 mg/g and Zn2+ 19·7 mg/g. Copyright © The Royal Society of Edinburgh 2012.