Per capita production (PCP) and composition of solid waste in different cities in developing countries
\\n\\n
Released this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\\n\\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'IntechOpen is proud to announce that 179 of our authors have made the Clarivate™ Highly Cited Researchers List for 2020, ranking them among the top 1% most-cited.
\n\nThroughout the years, the list has named a total of 252 IntechOpen authors as Highly Cited. Of those researchers, 69 have been featured on the list multiple times.
\n\n\n\nReleased this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\n\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
\n'}],latestNews:[{slug:"stanford-university-identifies-top-2-scientists-over-1-000-are-intechopen-authors-and-editors-20210122",title:"Stanford University Identifies Top 2% Scientists, Over 1,000 are IntechOpen Authors and Editors"},{slug:"intechopen-authors-included-in-the-highly-cited-researchers-list-for-2020-20210121",title:"IntechOpen Authors Included in the Highly Cited Researchers List for 2020"},{slug:"intechopen-maintains-position-as-the-world-s-largest-oa-book-publisher-20201218",title:"IntechOpen Maintains Position as the World’s Largest OA Book Publisher"},{slug:"all-intechopen-books-available-on-perlego-20201215",title:"All IntechOpen Books Available on Perlego"},{slug:"oiv-awards-recognizes-intechopen-s-editors-20201127",title:"OIV Awards Recognizes IntechOpen's Editors"},{slug:"intechopen-joins-crossref-s-initiative-for-open-abstracts-i4oa-to-boost-the-discovery-of-research-20201005",title:"IntechOpen joins Crossref's Initiative for Open Abstracts (I4OA) to Boost the Discovery of Research"},{slug:"intechopen-hits-milestone-5-000-open-access-books-published-20200908",title:"IntechOpen hits milestone: 5,000 Open Access books published!"},{slug:"intechopen-books-hosted-on-the-mathworks-book-program-20200819",title:"IntechOpen Books Hosted on the MathWorks Book Program"}]},book:{item:{type:"book",id:"724",leadTitle:null,fullTitle:"Crosstalk and Integration of Membrane Trafficking Pathways",title:"Crosstalk and Integration of Membrane Trafficking Pathways",subtitle:null,reviewType:"peer-reviewed",abstract:'Membrane traffic is a broad field that studies the complex exchange of membranes that occurs inside the cell. Protein, lipids and other molecules traffic among intracellular organelles, and are delivered to, or transported from the cell surface by virtue of membranous carriers generally referred as "transport intermediates". These carriers have different shapes and sizes, and their biogenesis, modality of transport, and delivery to the final destination are regulated by a multitude of very complex molecular machineries. \nA concept that has clearly emerged in the last decade is that each membrane pathway does not represent a close system, but is fully integrated with all the other trafficking pathways. The aim of this book is to provide a general overview of the extent of this crosstalk.',isbn:null,printIsbn:"978-953-51-0515-2",pdfIsbn:"978-953-51-5272-9",doi:"10.5772/1233",price:119,priceEur:129,priceUsd:155,slug:"crosstalk-and-integration-of-membrane-trafficking-pathways",numberOfPages:260,isOpenForSubmission:!1,isInWos:1,hash:"c561b7ed6d78b9970230aa82a71e8561",bookSignature:"Roberto Weigert",publishedDate:"April 11th 2012",coverURL:"https://cdn.intechopen.com/books/images_new/724.jpg",numberOfDownloads:20833,numberOfWosCitations:14,numberOfCrossrefCitations:10,numberOfDimensionsCitations:18,hasAltmetrics:0,numberOfTotalCitations:42,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"March 7th 2011",dateEndSecondStepPublish:"April 4th 2011",dateEndThirdStepPublish:"August 9th 2011",dateEndFourthStepPublish:"September 8th 2011",dateEndFifthStepPublish:"January 6th 2012",currentStepOfPublishingProcess:5,indexedIn:"1,2,3,4,5,6",editedByType:"Edited by",kuFlag:!1,editors:[{id:"82699",title:"Dr.",name:"Roberto",middleName:null,surname:"Weigert",slug:"roberto-weigert",fullName:"Roberto Weigert",profilePictureURL:"https://mts.intechopen.com/storage/users/82699/images/2126_n.jpg",biography:"Roberto Weigert is a principal investigator at the National Institutes of Health (NIH). 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In 2006 he established the Intracellular Membrane Trafficking Unit at the National Institute of Dental and Craniofacial Research where he has developed novel microscopy-based technologies to study the patho-physiology of the oral cavity.",institutionString:null,position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"1",institution:{name:"National Institutes of Health",institutionURL:null,country:{name:"United States of America"}}}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"418",title:"Membranology",slug:"membranology"}],chapters:[{id:"35242",title:"Semi-Intact Cell Systems - Application to the Analysis of Membrane Trafficking Between the Endoplasmic Reticulum and the Golgi Apparatus and of Cell Cycle-Dependent Changes in the Morphology of These Organelles",doi:"10.5772/31440",slug:"semi-intact-cell-system-application-to-study-the-membrane-trafficking-between-the-endoplasmic-reticu",totalDownloads:1938,totalCrossrefCites:1,totalDimensionsCites:1,signatures:"Masayuki Murata and Fumi Kano",downloadPdfUrl:"/chapter/pdf-download/35242",previewPdfUrl:"/chapter/pdf-preview/35242",authors:[{id:"87135",title:"Prof.",name:"Masayuki",surname:"Murata",slug:"masayuki-murata",fullName:"Masayuki Murata"},{id:"87195",title:"Dr.",name:"Fumi",surname:"Kano",slug:"fumi-kano",fullName:"Fumi Kano"}],corrections:null},{id:"35243",title:"Mophogenesis and Dynamics of Post-Golgi Transport Carriers",doi:"10.5772/39204",slug:"mophogenesis-and-dynamics-of-post-golgi-transport-carriers",totalDownloads:1252,totalCrossrefCites:0,totalDimensionsCites:0,signatures:"Roman S. 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Since recycling is seen as the most promising and cost-effective option to reduce the use of fossil energy and non-regenerable raw materials, in the industrial concept and present trends in the oxidic materials applications, geopolymers seem to meet all the criteria to replace conventional materials and contribute to a sustainable future. By applying innovative technologies, the coefficient of use of waste for developing new materials can be increased simultaneously with the decrease of the carbon footprint and the ecological impact. Accordingly, these eco-friendly materials will participate in cutting-edge research and applications due to their tailored properties, including superabsorbent capacity, heavy metals encapsulation, flame retardancy, mechanical performance, electrokinetic behaviour, corrosion resistance and thermal properties.
\r\n\r\n\tThis book aims to join activities and knowledge of researchers from multiple fields, in order to obtain a key overview in the advances in geopolymers synthesis and characterization, including base chemistry concepts, nanoscale characterization and applications in top-level industry.
\r\n\r\n\tThe topics are described as follow, but are not limited to:
\r\n\t1. Geopolymers chemistry topic describes the chemical reaction models and chemical kinetic of the geopolymerization which occurs after mixing the aluminosilicate raw materials with an alkaline solution.
\r\n\t2. Advanced characterization of geopolymers topic includes innovative technologies applied on geopolymers characterization at the nanoscale level, meant to explain the bond between the reacted and nonreacted particles from the composition.
\r\n\t3. Sustainability with geopolymers topic should provide clear information about the characteristics and applications of the geopolymers which use as raw materials industrial waste. Moreover, environmental impact studies which offer a clear view of the effects produced by geopolymers manufacturing, compared to conventional materials, is included.
\r\n\t4. Geopolymers as functional materials topic will present key aspects in developing geopolymers with tailored properties that increase further the heavy metals adsorption capacity, offering outstanding opportunities for energy-efficient separations and process intensification, in terms of saving energy, reducing capital costs, minimizing environmental impact and maximizing the raw materials exploitation.
\r\n\t5. Reinforced structures topic describe the effects produced by the introduction, in the geopolymers matrix, of different types of reinforcing elements.
Municipal solid waste (MSW) is the most complex solid waste stream (Troschinetz & Milhecic, 2009). The search forsustainable development and in particular factors such as fast population growth, land limitations and difficultiesassociated with finding suitable sites for establishing landfills, as well as the decrease of raw materials, make thatpractices for the management MSW traditionally used in developing countries such as collection and final disposal, becomplemented with recycling as a preferable option for dealing with the solid waste generated.This position has been promoted in international events such as the Johannesburg Summit on Sustainable Development,in which the recycling and reuse of waste were identified as key strategies for the accomplishment of the main objectivesand essential requisites for a sustainable development, since it contributes to reduce the negative effects on theenvironment and increases the efficiency of the use of resources (United Nations, 2002). From this perspective, there arenotable efforts made in developing countries such as Tanzania (Mbuligwe et al., 2002), Colombia (Minambiente, 2002)and Botswana (Ketlogetswe & Mothudi, 2005), where policies that give priority to recycling immediately after sourcereduction have been enforced; however, the application level of these policies is variable and final disposal on the land still remains asthe primary option with significant application (Fricke et al., 2001; OPS, 2005; UNEP, 2008).
The data in Table 1 show per capita production and composition of solid waste in different cities in developing countries.In all cases there are significant proportions of putrescible waste in the form of food and yard wastes. The dependency onagriculture for subsistence and economical development of these countries, as well as conservation requirements for soilquality, the productivity and gradual increase of the costs of mineral fertilizers, generate the necessity of using alternativesoil amendments. In this sense, the organic matter and nutrients contained in the putrescible fraction of solid wasteconstitute a viable alternative for this situation (Diaz et al., 2007). Another element that can stimulate the recycling ofthese wastes is the reduction in the production of greenhouse gases (GHG) compared with traditional techniques of finaldisposal. Barton et al., (2008) compared the generation of carbon dioxide in final disposal systems at open dump andsanitary landfills (considering three forms of managing emissions) with alternatives such as composting and anaerobicdigestion with electricity production, finding that in the open dumpsites and sanitary landfills, emissions varied between0.09 and 1.2 tCO2e/t, whereas in composting the emissions were neutral and in the anaerobic digestion plant it was -0.21tCO2e/t; however, costs of the last option limit significantly its applicability.
City | PCP (Kg/cap-day) | Putrescible | Paper | Metal | Glass | Plastic, rubber and leather | Textiles | Ceramics, dust and stones |
Bangalore, India1 | 0.4 | 75.2 | 1.5 | 0.1 | 0.2 | 0.9 | 3.1 | 19.0 |
Manila, Philippines1 | 0.4 | 45.5 | 14.5 | 4.9 | 2.7 | 8.6 | 1.3 | 27.5 |
Asunción, Paraguay1 | 0.46 | 60.8 | 12.2 | 2.3 | 4.6 | 4.4 | 2.5 | 13.2 |
Mexico City, Mexico 1 | 0.68 | 59.8a | 11.9 | 1.1 | 3.3 | 3.5 | 0.4 | 20.0 |
Cali, Colombia 2 | 0.39 | 65.54 | 6.23b | 1.06 | 2.56 | 11.12 | 1.98 | 11.51c |
Per capita production (PCP) and composition of solid waste in different cities in developing countries
In the same manner, other materials with reuse potential such as different types of paper, metal, glass and plastics generally represent morethan 6% of the MSW generated. Taking into account that most of the developing countries do not have one or more of theraw materials (e.g. iron ore, bauxite or petroleum of importance for its economical development) or other substitutematerials, reuse of these materials also is an option (Diaz et al., 2007).
In this article a description and analysis of the application of the options for recovering resources from MSW in differentregions of developing countries, identifying common elements that favor or limit the application of these and suggestingalternatives that contribute to the sustainability, is made. The approach is carried out from the Integrated SustainableWaste Management concept, which proposes to have a vision of the situation that involves the stakeholders, the components of the wastesystem and sustainability aspects that determine the functioning of the systems to reach technically appropriate,economically viable and socially acceptable solutions that do not degrade the environment (Van de Klundert&Anschutz,2001). Also, this article focuses in recycling and composting since both of these alternatives constitute the options with the highest degree of application providing an overview of the findings reported by several authors worldwide, withexperiences in countries or regions in Africa, Asia and Latin America and the Caribbean (LAC).
In developing countries it is acknowledged that the recovery of materials such as iron, steel, copper, lead, paper plasticand glass will decrease the investment in importing these materials and save energy (Kocasoy, 2001); however, properrecovery is scarcely applied. Some of the reasons for this situation are: shortage of properly trained professional, absenceof appropriate technology, poor public awareness and the relatively high initial capital investments costs required for theirimplementation. Although a few large-and medium-scale solid waste treatment facilities – imported from industrializedcountries, have been built and operated, the intensive mechanical and energetic requirements of these technologies havefinally driven most of these facilities to be shut down (Diaz et al., 2002). On the other hand, the prices obtained for some of therecovered materials typically are lower than the segregation / reprocessing costs, which can be even higher than thecosts of virgin materials, so that recycling activities usually have to be subsidized, except for materials such as aluminumand paper (Bogner et al., 2007). Table 2 shows the waste recycling rates in some developing countries.
Country/region | Recycling rate of municipal waste (%) | ||||
Glass | Metal | Paper | Plastic | Total | |
LAC1 | 0.8 | 2.1 | 2.0 | 3.4 | |
Brazil2 | 41 | 30 | |||
China2 | 7- 10 | ||||
Colombia3 | 10 | ||||
Nepal2 | 5 | ||||
Thailand2 | 18 | 39 | 28 | 14 | 15 |
Turkey2 | 25 | 30 | 36 | 30 | |
Vietnam2 | 13-20 |
Recycling of waste in developing countries/regions
Waste recovery practices generally are carried out in an informal manner mainly by scavengers on the streets and at finaldisposal sites, under inadequate working conditions. The formal sector has concentrated on the collection and finaldisposal; although recycling is viewed as an option, its application is very weak. In the same way, the attitude of theformal waste management sector towards informal recycling often is very negative regarding it as backward, unhygienic andgenerally incompatible with modern waste management systems (Wilson et al., 2006). Nevertheless, recycling ratesreached by the informal sector in several countries are quite high, fluctuating in a range of 20% - 50%, values that arecomparable to those achieved by modern waste management systems in industrialized countries (Wilson et al., 2009).
In Africa there are few formal systems for material recovery instituted by public agencies or the private sector. Recovery ofmaterials, including source separation and recycling is carried out mainly by the informal sector. This activity is centeredon materials of economic and/or social value; plastic bags, bottles, paper, cardboard and cans are reused before enteringthe waste chain. A few materials are converted into new products for local use; some examples are the smelting ofaluminum cans and scrap metals into household utensils, and paper and plastic residues into products for tourists (Otieno& Taiwo, 2007).
In Kenya, recycling has gained importance due to the increasing costs of raw materials. Initially it was carried outinformally by impoverished people, but it is now emerging at an industrial level (Rotich et al., 2006). In Cameroon,governmental policies establish strategies for environmental protection and promotion of conservation of materialsthrough an adequate disposal and recovery of MSW; however, in practice management is focused on, collection anddisposal on the land (Manga et al., 2008).
In Nigeria, although SWM is identified as one of the environmental elements to include in the Poverty Reduction Strategy,characterization studies carried out in the central part of the country indicate that the recyclable materials contained in thesolid waste do not warrant investment in recycling as a waste management approach (Sha’ Ato et al., 2007). In Lagos,recycling and resource recovery exist, but have not received the attention of the government and the waste managementauthorities. It is estimated that approximately 5- 8% of MSW are recycled through refuse dealers, who separate thematerials and sell them to consumers, as well supply them to mills and factories (Kofoworola, 2007).
In Botswana, most of the local companies dedicated to recycling are only in charge of collection, the recovered materialsare exported to different countries such as South Africa and Zimbabwe. The amount of recyclable materials recovered infinal disposal sites is taken as an indication of the potential for developing a recycling industry on a large scale at the locallevel (Ketlogetswe & Mothudi, 2005).
In the Southern and Western regions of Asia, industries that deal with repairing items and with used products areimportant sources of recovery and reuse of waste. In the cities of low or medium income of the East and Pacific regions,informal source separation and recycling have been a common practice for many years; gathering, trading, and reprocessing materials isthe work of many people (UNEP, 2008). In the East this activity is generally carried out by medium- scale or householdenterprises, and is predicted to grow where it offers economical benefits (Nguyen Ngoc & Schnitzer, 2009).
In Jordan, recycling is carried out by scavengers in final disposal sites and through formal systems managed by themunicipalities or NGO’s; scavengers usually search for cardboard, tins and plastic bottles. Experiences managed by municipalities include recovery of recyclables from the solid waste stream prior to landfilling and a pilot material recycling facility (Abu Qdais, 2007). In the case of the Gulf Co-operation Council States (Kuwait, Saudi Arabia, Bahrain, Qatar, United Arab Emirates y Oman), Alhumoud (2005) affirms that most of the countries do not report recycling goals or programs and the only comprehensive form of recycling available is the recycling of paper and cardboard; a limited amount of recyclable materials such as cans, metals and cardboard are collected from the waste containers in front of the houses by scavengers. In a research project conducted in seven Palestinian districts there was no evidence of reuse and recycling programs, identifying only the informal recovery of metal scrap from waste collection containers and dump sites (Al-Khatib et al., 2007).
In Pakistan, although in the last four decades the generation of waste has increased significantly, there are not specificrecycling programs on a country-wide scale or in the big cities. In Lahore, 1.97 million tons of waste are generatedannually, of which 65% to 70% are collected; approximately 0.04 million tons are sold directly to industry; householdsreuse around 0.054 million and 0.09 million of recyclables are commercialized at junkshops by scavengers andhouseholds annually. It is estimated that 21.2% of the total recyclable waste is being used for recycling, generatingaround US$ 4.5 million a year (Batool et al. 2008).
In Ankara (Turkey), recyclable materials constitute around 18% of the total solid waste generated; Government StatisticsInstitute estimates that scavengers are collecting up to 50% of these materials. It is considered that the average incomefrom recyclables is between US$ 25.000 - 50.000 per day; however, the income per scavenger is between US$80 andUS$100 per month and about US$20,000 is for the owners the recycling system each day (Ali, 2002).
In China, MSW seems to revolve around small scale operations as a result of the application of the principle that thepolluter is responsible for treatment and disposal. As a general rule there are not treatment operations only small- scaleand inefficient plants (Suocheng et al., 2001); however discarded material is imported from different countries on a largescale for reuse and recycling, generating around 5000 enterprises, about 1.4 million jobs, with recovery rates of 85%,47%, 25%, 20% and 13% in materials such as iron and steel, rubber, plastics, paper and glass, respectively (Shekdar,2009).
In the case of Latin America and the Caribbean (LAC), the Pan-American Health Organization PAHO (2005) indicates that the nature of the solid wastes,particularly those generated in residential, commercial and institutional sources, creates a technological problem for theapplication of recycling since its quality is affected by the mixture of materials. In all the countries of the region informalsegregation is common practice and a frequent source of income for the impoverished and unemployed fraction of thepopulation. In Colombia, Mexico, Brazil and Venezuela recycling programs of considerable magnitude have beenextended to the communities in order to promote the organization in cooperatives and private associations (Minambiente,2002). Esteban García et al. (2001) point out that the recycling activity is a well established reality in the region, whichreflects in the acknowledgment through names such as “cirujas” in Argentina, “buzos” in Bolivia, “cachureros” in Chile and“pepenadores” in Mexico. They also indicate as an example in Latin America, that in Mexico the informal sector iscomposed of people who work in dumpsites and in areas not covered by the collection service, as well as people from the middle class and part -time scavengers (students, retired persons and housewives, who obtain additional income).
McBean et al. (2005) report that through the training and organization of the informal sector, in Tucuman (Argentina) hasbeen possible to recover significant percentages of materials such as paper and newsprint, and plastic (4.3 and 27.2%respectively), making it possible for the people involved in this activity to earn an income 1.75 times the minimum wage inthat region. In LAC, more than an impediment, recycling cooperatives represent an opportunity for the private sector andindustries to increase the market and level of recycling (Lopes et al., 2007).In an assessment carried out by Do Prado Filho and Sobreira (2007) at 29 recycling-composting plants located in thestate of Minas Gerais (Brazil), it identified infrastructure, operation and location conditions that allow to rank 95% of thesesites as adequate or acceptable; however, the working conditions of the workers were ranked as regular in 13 and as badin the rest of them. In the same way, it was also determined that in all of the cases it is feasible to sell the recycledmaterials.
The topics discussed in the previous paragraphs allow to affirm that recycling of some components of the waste stream constitutes a source of incomegeneration and materials recovery, with market for the products that require the development of programs that integratethe actors involved in recycling and technological advances that take into account the local labor potential to improve thequality of the processes and products.
Composting is described as an economically viable method compared with other processes and also effective incontributing to the reduction in the amount of material that should be taken to the landfill (Barreira et al., 2006). However,although successful experiences have been reported in its application (Mbuligwe et al., 2002; Zurbrügg et al., 2005,Bezama et al., 2007) it is acknowledged that there are important limitations (Zurbrügg et al., 2005, Barreira et al., 2006,Körner et al., 2008). Dulac (2001) pointed out that the high organic content of the waste streams of developing countriesis ideal for composting, but municipal services operators do not have enough and adequate information and even thoughthey may be familiar with the application of composting in agriculture, it is not considered as a way to solve their urbanwastes problems. Bogner et al. (2007) indicate that labor-intensive processes are more appropriate and sustainable forthose countries than highly mechanized technological alternatives at large-scale operations.
In Africa, composting has failed in cities such as Dakar (Senegal) y Abidjan (Cote d´Voire), due to the lack of demand for the final product. International NGO’s have subsidized small scale composting in countries such as Benin, Cameroon,Kenya, Nigeria and Zambia, without making a significant impact in the reduction of MSW going to the landfill. The problemwith composting in African cities is the low quality of the product due to the inadequate segregation of the wastes, whichresults in a low demand (Otieno & Taiwo, 2007). In Kenya, some groups compost food wastes that are sold to urbanfarmers and landscapers (Rotich et al., 2006).
In Southeast Asian Nations, composting is not a common practice due to high operation and maintenance costs, the high cost of the final product with respect to commercial fertilizers, and the available market, so that the activity is supported by governments (Nguyen Ngoc & Schnitzer, 2009). Alhumoud (2005) points out that in the Gulf Co-operation Council States in the last 20 years municipalities have concentrated on composting as an alternative for the treatment of MSW in spite of the failure of a large number of plants in the region. This author also affirms that the main problems with these plants have been the poor performance, high operating and maintenance costs, lack of technical support and inefficient management. In Jordan, even with a high fraction of biodegradable organic solid waste generated in the country and the fact that 91% of the country land is arid to semiarid, composting has not been considered as an option for solid waste management (Abu Qdais, 2007).
Hui et al. (2006) indicate that although composting is a widely utilized practice in Western countries, in Chongquing, oneof the four largest municipalities in China, it is rarely used due to reasons such as the low application of sourceseparation, low acceptance of compost by farmers, limited usefulness of compost in comparison with chemical fertilizersand strict regulations, monitoring and quality standards of the product. In India, composting is a tradition mainly in ruralareas; utilization of large-scale and centralized composting plants during the 1970´s had not been economically feasible.Studies have determined that compost is difficult to use because the waste arrives mixed and with high quantities orinorganic materials (Narayana, 2009).
The cooperation with NGO’s, the supply of free bins for organic materials and the governmental support for theinvestment have had a high correlation with the better performance of composting in Thailand (Suttibak & Nitivattananon, 2008).
In LAC, the percentage of recovered waste reaches figures of only 2.2% out of the total and even with the predominanceof organic matter; the application of composting is carried out at small scale, reaching only 0.6% of these wastes. Theproblem does not end with the scarce application of reuse, recovery and recycling technologies, it transcends to the lackof trust and the unsuccessful application of these technologies. From the beginnings of the 70´s several initiativesoriented to the establishment of composting plants with diverse imported technologies have failed due to factors relatedmainly with the inefficient maintenance of equipment, indetermination of markets, inadequate technologies and lack oflinking with strategic environmental projects (OPS, 2005), which shows the necessity of conceptual and technologicaldevelopments contextualized in the reality of the region.
In the case of Cuba, Körner et al., (2008) pointed out than only one facility for composting of MSW is known, and thatcomposting this kind of waste has not been reported officially as a treatment alternative; however its implementation isanticipated by the government.
Fricke et al. (2001) affirm that from 23 composting plants implemented in Brazil only 6 were in operation and that many of those plants were decommissioned after a short period of operation due to reasons such as unsatisfactory operation, high operational costs and low quality of the compost, low materials recovery and nauseous odors. In the monitoring reports of the quality of the compost produced in 20 recycling-composting plants assessed by Do Prado Filho and Sobreira (2007) is brought into focus the presence of heavy metals in variable amounts, which restricts the use compost in the soil. They also indicate that in these reports is rarely included the technical concept conclusive on the figures obtained for each parameter, the analytical methods used and the reference values as to the quality of the material and also that in spite of the presence of trained personnel for the operation of the plants there is considerable difficulty in understanding the results of the analysis of the quality of the products.
In Colombia, the Superintendencia de Servicios Públicos Domiciliarios (SSPD, 2008), determined that there were 28 MSW facilities that dealt with processing the putrescible fraction of MSW, from which 54% carried out composting, 15%vermicomposting and the remaining 31% used both methods. The processing time of the plants varied between 30 and180 days, obtaining an average production efficiency of 33% (with respect to the material subjected to processing) andalthough quality control was not carried out, the obtained products were being utilized by farmers of different vegetablespecies and food without knowing the sanitary risk this could represent.
The scenarios previously presented contrast with the economical, social and environmental potential that the recovery, reuse andrecycling of waste has had in regions such as Dhaka -Bangladesh (Zürbrugg et al., 2005), Dar es Salaam –Tanzania(Mbuligwe et al., 2002), Yala -Thailand (Mongkolnchaiarunya, 2005) and Turkey (Metin et al., 2003), where practicessuch as composting and recycling, besides the sanitary and environmental benefits of the reduction of the amount ofmaterials to be disposed in the land, generate job opportunities and income generally for the sectors with the lowest economicalcapacity.Reported experiences by Zürbrugg et al. (2005) and Körner et al. (2008), for Bangladesh and Cuba respectively, indicatethat the application of composting has had better success at small-scale and in decentralized facilities, but frequentfailures are present in the marketing of the product. Drescher & Zürbrugg (2006) suggest that for the large cities, thecombination of decentralized small- scale composting systems with medium- scale centralized composting schemesconstitute an ideal strategy for the management of organic wastes; at the same time, decentralized composting systemsare enough for small municipalities.
The use in agriculture, as soil conditioner or fertilizer, is one of the most usual ways to take advantage of the compostobtained with the processing of MSW; however the quality of the product is subordinated to variables such as the design of the compostingfacility, type and proportions of feedstock used, composting procedure and maturation period (Hargreaves etal.,2008) the evaluation of alternative techniques for improving and/or facilitating the monitoring of the process andquality of the product (Said-Pullicino et al., 2007, Barrena et al., 2008) that deserve to be assessed in more depth.
Recent studies conclude that amongst the main factors for the sustainability of the reuse and recycling systems are wastecollection and segregation, MSW management plan, and a local market for the recycled materials (Troschinetz &Milhecic, 2009). To accomplish the sustainability, it is necessary to develop production and marketing strategies with amarketing vision that acknowledge and integrate the formal and informal sectors, requiring important agreementsbetween stakeholders, the adaptation of educational schemes and technological options, the identification and positioningin the market and the setting of normative references.
At the same time, although the knowledge of the quantity and quality of the materials to be processed is one of the key elements for guiding the industrial vision, it is recognized that the lack of reliable studies on the composition and generation of waste constitute one of the main limitations for the management (Diaz et al., 2002). This situation could be related with the cost and complexity of the methodological procedures used for the execution of such studies (Hristovski et al., 2007). It is necessary to structure alternative methodological schemes that take into account limitations of the trained personnel and the low availability of financial resources, which can be successfully applied. In this aspect, there are some positive experiences in Santiago de Cali in Colombia, where a sampling and characterization program that involved the participation of local stakeholders was structured, adapting a method that utilizes one block as the sampling unit, obtaining results with high confidence levels and low errors, with affordable costs for the local conditions (Klinger et al., 2009).
It is also important to conduct efforts that allow all the stakeholders in the management chain to identify the waste as anelement with possibilities of reuse and not as garbage, term associated with problem. At the same time, aspects such asthe deterioration of the quality and loss of value of the materials to reuse, which starts at the point of generation and in thecollection vehicles, must be avoided. The encouragement of practices such as source separation and separate collectionare options with the potential to solve this situation; however, in this way additional costs for the user or for industry canbe generated, encouraging the informal recovery which creates conflicts with personnel from the collection system.Analysis and local agreements that take into account these situations and identify a solution must be developed.
In the same way, it is necessary the research and development of technological options that facilitate the transformationin situ, allowing amongst others, the use of locally available resources for the operation and maintenance, as well as thereduction of volumes of materials and the consequent decrease in transportation costs, increasing the added value of thereuse of these products. In this sense, an alternative is the realization of adaptations of the technologies utilized for therecovery of industrial wastes, taking into account the quality and quantity of the MSW. It is also important to put intopractice monitoring schemes and quality control of the products since the complexity and costs associated with thosetraditionally used limit its application.
The previously mentioned situations demonstrate that the sustainability of the reuse of the MSW transcends technical andeconomical aspects and that it is necessary to think of it as a system. Then, a reuse system is a set-up of parts orinterrelated elements that have as a function the efficient reincorporation of recovered materials from solid waste to theeconomical and productive cycle. Reuse system is maintained in time through technically appropriate and economicallyand socially feasible strategies, without threatening natural resources for future generations.
The reuse of waste can support dignified work for many people, the conservation of non-renewable natural resources andthe reincorporation of products into the productive cycle in developing countries, for such reason its sustainability must be agoal for its human and sustainable development.
In developing countries, recovery is an alternative identified and/or applied as a solution to the problems associated withsolid waste management. However, it requires that recovery be developed as an option with sustainability potential. Forthat, it is indispensable the participation of stakeholders and their integration with technologies and markets.
A key element for the sustainability of the reuse systems is the articulation of efforts and the mutual acknowledgementbetween the formal and informal sectors. The informal sector is one of the main elements of the recovery of paper,plastic, metals and glass, carrying it out generally under precarious working conditions and with inefficient technologies,making necessary the adaptation or development of technologies that favor the employment of local labor, dignifying theirworking conditions and under economical and sustainable conditions.
The valorization of waste as being an opportunity and not as something to be discarded by the generators is fundamental, so that not onlythe environmental but also the social and economical benefits associated with the reuse must be recognized, from thesebenefits also the generator must feel itself as a key part of the solution.
For the implementation of reuse systems from MSW it is important to obtain reliable estimates of the quantity and compositionof the materials to take advantage of, as well as the characteristics and markets of the products. In the event of thenecessity of a central installation for the reuse operations, siting, design and operation must be adapted to the localconditions.
In recent years, there have been rapid growth predictions for polypropylene-based composites, due to their applications in many fields such as automotive, home appliances, and construction industries [1, 2, 3, 4, 5]. Since the last decade, several nanoparticles have been incorporated into polypropylene and other thermoplastics as reinforcements, to produce stronger and lighter polymer composites [5, 6, 7, 8, 9]. There are many different thermoplastic polymers available on the market today such as polypropylene, polyethylene, etc. Amongst these, polypropylene (PP) is one of the most widely used polymers due to the fact that it is inexpensive and offers attractive properties (rigidity, light weight, thermal and chemical stability, etc.); however, it has the disadvantage of being relatively brittle at room temperature and exhibiting poor resistance to crack propagation. Many investigations have been reported on fracture properties of polypropylene. It has thus been shown that fracture toughness of PP increases with increasing molecular weight and decreasing crystalline percentage. The temperature at brittle-ductile transition of PP has also been reported to increase with increasing crystallinity [10, 11, 12, 13]. Most properties of polymers can be altered through the addition of fillers. Recent polymer nanocomposites have been an area of intense research because of their potential applications as multifunctional and high-performance materials. These nanocomposites are fabricated by simply adding small amounts of nanoparticles in the polymer matrices. The general class of nanocomposite is the mixture of organic and inorganic materials. Significant effort is focused on the ability to obtain control of the nanoscale structures via innovative synthetic approaches. This is a rapid growing area of research and is expanding as it generates many new exciting materials with various properties. These properties of nanocomposite materials depend not only on the properties but also on their morphology and interfacial characteristics. The nanoparticles significantly enhance the mechanical properties, thermal stability, reduced gas permeability, and other physicochemical properties [14, 15, 16, 17, 18, 19] of the neat polymer. To change the properties of these composites, relatively small amounts of the nanoparticle are needed, more often the percentage by weight (0.5–5%) which results from the particles having incredibly high surface to volume ratios.
\nSince the discovery of nanoparticles, researchers are aiming to achieve a uniform particles-polymer interaction rather than the polymer-polymer or particle-particle interaction to obtain the maximum benefit. Wetzel et al. [20] incorporated various amounts of Al2O3 nanoparticles into a polymer matrix and studied the influence of nanoparticles on the flexural strength, impact energy, dynamic mechanical thermal properties, and block-on-ring wear behavior, and their results show the improvement in nanocomposites as compared to the neat polymer. Zheng et al. [21] employed high frequency ultrasonic and mechanical procedures to disperse spherical SiO2 in epoxy resin. The results indicated that with the addition of 3 wt% of SiO2 into the resin, the tensile strength improved by 114%, the stiffness improved by 13%, and the impact strength improved by 56%. Wang’s et al. [22] reported that the dispersion of TiO2 nanoparticles was coated by an acrylic acid (AA)-plasma-polymers in a glycol solution, and results indicated that the dispersion of TiO2 nanoparticles were greatly improved after AA-plasma-polymer coating. They noted that the surface energy played a vital role in the dispersion behaviors of TiO2 nanoparticles. It is an effective way to improve the dispersion of nanoparticles by changing their surface energy by plasma polymer coating. Dai et al. [23] synthesized β-SiC nanorods using the reaction of carbon nanotubes by using a mixture of Si and I2 or through the use of a volatile SiO2. In this study, there was a large quantity of β-SiC nanorods prepared which was wrapped with uniform amorphous SiO2 layers on the outside surface. The formation of β-SiC nanorod was based on the carbothermal reduction of silica xerogels with carbon nanoparticles embedded in the network, and the formation of SiO2 layer was from the reaction of decomposed SiO and O2.
\nExtrusion is one of the most widely used processing techniques for fabrication of thermoplastic polymers. It can be used as a “stand alone” machine to directly shape parts or it can also be used as a melting device that is coupled with other secondary shaping devices. The two main advantages of this process over other manufacturing processes are its ability to create very complex cross-sections and work materials that are brittle, because the material only encounters compressive and shear stresses. It also forms finished parts with an excellent surface finish [24, 25]. Extrusion is also used in the dispersion of nanoparticles to prepare polymer nanocomposites. Mohammed et al. [26] investigated the effect of SiO2 infused into nylon-6 at wt% of 0, 1, and 2, respectively, and extruded into filaments. Experimental results showed that by infusing nanoparticles into nylon −6 and extruding it increased its tensile modulus, yield strength, hardening modulus, and ultimate tensile strength. There was a 45% enhancement in tensile modulus and a 26% enhancement in ultimate tensile strength observed in the 2 wt% system while compared to the neat nylon-6. TGA results indicated more thermal stability found in the nanophased infused systems, while the DSC studies indicated a more moderate increase in Tg. Liu et al. [27] presented the effects of incorporated montmorillonite (MMT) on a surface and the bulk mechanical properties of as-synthesized polyamide-6/montmorillonite (PA6/MMT) composites that were prepared using the twin-screw extruder mixing technique. Russo et al. [28] studied the effect of multiple extrusions on nanostructure and properties of nylon 6 nanocomposites. These researchers produced nanocomposites at different silicate loadings by melt compounding and submitted to further reprocessing by using single and twin screw extruders. Rheological, morphological, and mechanical analyses were carried out on as-produced and reprocessed samples to explore the influence of the number and the type of extrusion cycles on silicate nanodispersion. The results obtained displayed that the reprocessing by single screw extruder can modify the initial morphology since the re-agglomeration of the silicate layers can occur. However, a better nanodispersion was observed in the hybrids reprocessed by twin screw extruder, which was a result of the additional mechanical stresses able to realizing a dispersive mixing that contributes to avoid re-agglomeration phenomena. The high shear stresses produced with twin screw geometry determined also a significant degradation of neat matrix, principally based on chain scission mechanism. All as-produced and reprocessed hybrids showed a substantial enhancement in tensile modulus with the adding of silicate. However, the entity of performance enhancements displayed by the reprocessed hybrids was found to be highly dependent on the degradation of both organoclay and polymer matrix as well as the silicate amount, the number, and the type reprocessing. Investigations were made by Yong et al. [29] on the effects of the coating amount of surfactant and the particle concentration on the impact strength of polypropylene (PP)/CaCO3 nanocomposites. These nanocomposites prepared with monolayer-coated CaCO3 nanoparticles had the best mechanical properties, including Young’s modulus, tensile yield stress, and impact strength because of the good dispersion of the nanoparticles in the polymer matrix, which in turn allowed them to study the effects of particle concentration on the impact strength of the nanocomposites. H-PP and E-PP, which were the low and high molecular weight PPs, respectively, were used as polymer matrices. Critical particle concentrations of 10 and 25 wt% corresponding to an abrupt increase in the impact toughness were determined for the E-PP and H-PP nanocomposites, respectively. Manolis et al. [30] observed a series of experiments which were performed on both simply supported and on-grade circular slab specimens, reinforced with different volumes of fibrillated polypropylene fibers in order to gauge its influence on the slab’s impact resistance and natural frequency. Literature survey clearly suggests that there have been studies on polymer systems infused with nanofillers, but there are no reports on combination of silicon carbide, silicon dioxide coatings infused into polypropylene. Herein, this study we report the effects of reinforcement of silicon dioxide coated silicon carbide nanoparticles in polypropylene thermal and mechanical properties.
\nThe nanoparticles used in these experiments were spherical silicon carbide, ~30 nm in diameter. The β-silicon carbide nanoparticles were purchased from MTI Corporation, Richmond CA, USA. These nanoparticles were then coated with four different types of silicon dioxide nanoparticles, colloidal (Nissan chemicals), 80 nm, and areosil (Degussa), and needle shaped SiO2 nanoparticles (Nissan chemicals). The colloidal silica solution MP-1040 was procured from Nissan Chemical Corporation. This filler is composed of 40% nanoparticles that are spherical in shape and approximately 200 nm in diameter dispersed in 60% of water. The 80 nm silica was procured from MTI Corporation Richmond CA, USA. These particles are spherical in shape having an 80 nm diameter. Areosil silica is also spherical in shape with a smaller diameter of approximately 5–15 nm and was also procured from Degussa. The other silica used was the needle shaped silica solution MP-1040 which was procured from Nissan Chemical Corporation. This filler is also composed of 40% nanoparticles and 60% water; however, these nanoparticles are irregular in shape.
\nThe matrix material used in this experiment is polypropylene procured from Chem Point. The polymer molecular weight ranged from 40,000 to 100,000, its powder diameter is approximately 20 μm, and the density of polypropylene is between 0.910 and 0.928 gr/ml. The melting point of polypropylene is 160°C with >50 isotactic crystalline structure. This type of high melting polymer can be molded or machined into structural components [31].
\nIn the first step, 250 mg of β-SiC was weighed and mixed along with 500 mg of powdered SiO2, 250 mg of pluronic F-127 and 60 ml of ethylene glycol. The reaction mixture was irradiated using high intensity ultrasound for 3 hours at 5°C under argon gas flow. This process was done for each of the two powdered types of SiO2; however for the solution types, when added to SiC nanoparticles, it was done using a weight ratio of 10:1. Upon completion of the sonication process, the silicon carbide coated silica nanoparticles were collected using a centrifuge at 12,000 rpm at 5°C for 30 min. The coated particles were washed 5 times, the first four times using distilled water and the last time with ethanol. The final step was to allow the sample to dry under vacuum for 24 hours at room temperature. Once dried, the coated nanoparticles were added to polypropylene at a ratio of 1:10 and then mixed using a Thinky mixer. The materials were placed in a special container and mixed under vacuum at 1200 rpm for 10 min. This step was done three times to ensure proper distribution of particles, before being extruded. This non-contact mixing method [32, 33] proves to be very efficient at dispersing nanofillers in polymer matrices without having any cross-contamination. This non-contact method works by independently revolving and rotating a container at various speeds in a planetary manner. As the container rotates, it experiences a number of forces that results in the material inside of the container being mixed. Centrifugal force presses the material outwards to the inner wall of the container, while other forces cause the material to move in a spiraling downwards direction along the slope of the container wall. The material then moves back to the center of the container and up to the top repeating the process and in turn mixing the sample. As the material circulates from top to bottom, it generates a kneading effect forcing trapped air out of the material.
\nIn the second phase, nanocomposites of polypropylene, silicon carbide/silicon dioxides were then extruded using a Wayne Yellow Label Top single screw extruder. The extruder has a 19 mm diameter screw, which is driven by a 2HP motor complete with a toothed timing belt for smooth speed reversal. Present are five thermostatically controlled heating zones that were used to melt the mixture before extrusion. Three of the zones were located inside the barrel and the final two were in the die zone set at respective temperatures of 340, 344, 350, 354, and 350°F. As the sample material passes through each zone, they are disintegrated into several branches and then combined again, which ensures proper distributive mixing of the nanoparticles and polypropylene. As the dispersed nanoparticles containing liquid polypropylene passes through the 10 cm long steel tube, it arrives to the die plate. As the sample passes through the extruder, it enters and completely fills the die, which in turn forms the flexure sample. The process schematic is shown in Figure 1.
\nFabrication of polypropylene/SiC/SiO2 nanocomposite.
JOEL-2010, High Resolution (Japan), Transmission Electron Microscopy (HRTEM), is used to study the size, shape, and extent of coating of SiC onto SiO2 nanoparticles. The samples were prepared by dispersing the nanoparticles in ethanol and placing a drop of the solution on a copper grid.
\nRigaku D/MAX 2100 X-Ray Diffractometer (Japan) was used to study the structural characteristics. The samples were prepared for XRD by uniformly spreading the nanoparticles on a quartz sample holder. The test samples were conducted from 0 to 80° of two theta at room temperature. Characteristics XRD diffraction patterns were collected and matched with established data from PDF files. X-ray diffraction helps to determine the crystallographic configuration of the coated nanoparticles and its nanocomposites.
\nThis surface analysis technique (2–10 nm analysis depth typically) XPS can identify elemental composition, oxidation state, and chemical bonding like covalent bonds (oxides, nitrides, etc.) by evaluating binding energy shifts. This test was done at Cornell University Dr. Jonathan Shu’s lab. The pressure in the analyzing chamber was typically 1.3 × 107 Pa under operating conditions. Photoelectrons were collected at approximately 45° from the specimen surface normal. The X-rays created photoemission electrons, and the signature of the photoemissions identified each element present in the samples.
\nThermogravimetric analysis was carried out using a Mettler Toledo (USA) TGA apparatus to find out the thermal stability of the test sample. This test is most commonly used to determine polymer decomposition temperatures, residual solvent levels, the amount of moisture content absorbed, and the amount of inorganic filler in polymer or composite material compositions. The samples were prepared by cutting the samples into small pieces, then placing 5 mg of the material in a platinum sample pan, and heating at a constant heating rate of 10°C/min from room temperature to 900°C under nitrogen atmosphere of 40 ml/min. The initial sample weight is measured at room temperature, and as heat is constantly being applied, the machine monitors the change in sample weight as a function of temperature. This result in weight loss versus temperature graphs being plotted from the data is obtained. In this case, the decomposition temperature is considered at 50% weight loss of the material.
\nDifferential scanning calorimetry (DSC) tests were carried out using a Mettler Toledo822e (USA) from 30 to 300°C at a heating rate of 5°C/min under a nitrogen atmosphere then cooled from 300 to 30°C at the same rate. These results were used in measuring the melting temperature and the crystalline temperature.
\nThree-point bending flexural tests were conducted using a Zwick Roell MTS (Germany) to evaluate the samples flexural properties. Ten samples were tested using ASTM D790-03 testing standards which are of nominal size 100 mm (length) × 12.5 mm (width) × 5 mm (thick) and a span/thickness ratio maintained at 16:1. The test were conducted at room temperature at a constant crosshead speed of 2.0 mm/min. Stress-strain plots were obtained as the load displacement data were recorded through the data acquisition system equipped with the Zwick Roell MTS machine.
\nXRD patterns were collected using a diffractometer operating in the Bragg-Brentano geometry utilizing Cu Kα radiation. The X-ray tube was operated at 40 kV and 30 mA. A 2θ scan range from 30 to 80° in steps of 20/min was recorded.
\nThe SiC coated onto various SiO2 samples were analyzed to investigate the effects of ultrasonic irradiation on the nanoparticles. The XRD spectra of pure SiC can be seen below in Figure 2(a). Through the use of the Jade 6.0 software, the peaks appearing at 2θ of 35.6, 41.5, 60.0, 72.0, and 75.5° indexed as (111), (200), (220), (311), and (222), designates the crystal spherical structured Moissanite-3C SiC (JCPDS 29-1129). The XRD of silicon carbide coating onto silicon dioxide was shown in Figure 2(b)–(e), and it is evident that all of the SiC particles are crystalline in nature and all assigned to β-SiC. The background wide peak pattern is the characteristic of an amorphous SiO2 phase. In the sample, the XRD data indicate the presence of only silicon carbide and amorphous silicon dioxide. The plot has characteristic peak intensities of FWHM, and d-spacing values which can be found in Table 1. A sharp peak around 35.6° corresponds to a spacing of 2.5189 A, which is attributed to the β-SiC (111) diffraction. There was an amorphous background present around 22° which is the result of the silicon dioxide presence. Deduced from the FWHM of β-SiC (111) diffraction peak. It is evident that, compared to pure SiC, the coated SiC FWHM peaks decreased significantly. In this case, the coated nanoparticles FWHM decreased compared to the neat, which results in coating of amorphous silica. The crystallite sizes of the particles were determined using Debye-Scherrer formula and FWHM method from the 100% peak of the pattern.
\nXRD patterns of SiC and coated nanoparticles.
Sample | \n2θ at 100% intensity | \nFWHM(°) | \nFWHM at 35.6° | \n
---|---|---|---|
SiC | \n35.612 | \n0.673 | \n0.673 | \n
Colloidal | \n35.746 | \n0.389 | \n0.612 | \n
Areosil | \n35.813 | \n0.397 | \n0.604 | \n
80 nm | \n35.694 | \n0.343 | \n0.674 | \n
Needle shaped | \n35.865 | \n0.368 | \n0.652 | \n
XRD analysis of SiC and coated SiC, FWHM.
The TEM micrograph in Figure 3 shows (a) as received SiC, (b) SiC coating on colloidal silica, (c) aerosol silica coated on SiC, (d) 80 nm silica coated on SiC, and finally (e) needle shaped silica coated on SiC. Figure 3(a) shows the SiC particles are spherical and particle sizes are about 30–50 nm. Figure 3(b) represents the coating of SiC on colloidal silica where the particles of silica are about 200 nm. The SiC particles are uniformly coated on silica spheres. Figure 3(c) shows that the particles of aerosol silica is coated on SiC nanoparticles. Since the aerosil silica is amorphous and also the particle sizes are about 5 nm, it is seen on the surface of SiC. In TEM Figure 3(d) and (e) shows the SiC particles and it was very hard to see the silica because of the silica is highly transparent to the electronic bean and difficult image.
\nTEM images of (a) SiC, (b) SiC coated SiO2, (c) SiC coated areosil, (d) SiC coated needle SiO2, and (e) SiC coated 80 nm SiO2.
XPS is a surface sensitive spectroscopic tool that provides information about chemical states and concentration of elements present in a sample with the exceptions of H and He. Each characteristic peak corresponds to the electron configuration of the electrons within the atoms, e.g., 1s, 2s, 2p, 3s, etc. This method uses soft X-rays to eject electrons from inner-shell orbital. The kinetic energy, Ek, of these photoelectrons is determined by the energy of the X-ray radiation, hν, and the electron binding energy, Eb, as given by:
\nUsing this technique, the surface of SiC and SiO2 were characterized from the surface to approximately 10 nm in depth. Each element shows a characteristic set of peaks in the photoelectron spectrum at kinetic energies of the elemental composition of the surface region determined by the photon energy and the respective binding energies. Elements exhibit binding energy peaks whose relative position depends on the electronegativity of their surrounding atomic neighbors. In the case of a phase mixture where more than one bonding state exists, a particular element is expected to have various binding energies, caused by different coordination/neighbor. The intensity of the peaks is related to the concentration of the element within the sampled region.
\nAs shown in Figure 4, it displays the XPS spectra of SiC/SiO2 nanomaterials. The most distinctive peaks present are the oxygen, carbon, and silicon peaks, respectively. Using the CasaXPS software for XPS analysis, a detailed spectrum of Si 2p, C 1s and O 1s of the chemical state of each element on the surface of the nanoparticles were identified and analyzed. Analysis of such element regions were done to confirm their attachment to the surface of the silicon dioxides. Silicon (Si 2p), carbon (C 1s), and oxygen (O 1s) elements can be found at binding energies of 102.8, 284.6, and 532.0 electron volts (eV), respectively. Also in Figure 4 above, one can take a look at the as received SiC which clearly shows a Si peak, but also shows where adsorbed contaminations like oxygen and carbon were found on the top layer within about 6 nm in thickness. This observation is consistent with other researchers [34, 35] and can be a result of the absorption of atmospheric oxygen. Figure 5(a) shows the high resolution scan of the deconvoluted XPS spectra of neat SiC for Si 2p peak and C 1s on the sub-surface layer. The spectra were Gaussian fitted based on the published data of the binding energies. The spectra emission line at binding energy (BE) of 100.47 eV is associated with the SiC bonding. In addition to this, two more fitted chemical shifts were observed at BE of 98.4 and 102.9 eV, which were identified as Si° and SiO2, respectively, for the spectra of SiC for Si 2p peak.
\nXPS spectra for neat SiC and coated nanoparticles.
Deconvoluted XPS spectra for SiC for (a) Si 2p peak (b) C 1s peak.
For the spectra of SiC, the C 1s spectrum was deconvoluted into three peaks (Figure 5(b) of BE 285.5, 282.7, and 289.06eV. The peak at 285.5 eV signified the presence of carbon in the form of hydrocarbon, while the peak at 282.7 eV is due to the binding energy of carbon in the form of SiC, and in the form of carbon bonded to oxygen, this was observed at 289.06eV. The binding energy for oxygen or O 1s was found to be 532.6 eV and can be associated either with O2-Si or C-O bonding which can be a result of surface contamination. From the surface chemical composition, it can be seen that the ratio of Si/C was found to be 0.29, which is much lower than the theoretical value for pure SiC of 0.5 which clearly indicates surface contamination.
\nThe coated hybrid nanocomposites of colloidal, areosil, 80 nm, and needle shape nanocomposites were also investigated using XPS for comparison with the neat sample. The chemical composition and binding energies were tabulated and presented in Table 2. The O/Si ratios from the table obviously doubled which indicated that surface contaminant oxygen was increased when SiC was sonicated with the four different types of SiO2. The concentration of C in the near surface decreases from 65.09% for neat SiC to an average of 43.26% for sonicated SiC in SiO2. This decrease is may be removal of carbon in the form of CO2. However, it can be seen here that, the as received SiC absorb oxygen which is enough to impart strong chemical double bonding in the system.
\nSamples | \nComposition (atomic %) at the surface of nanoparticles | \nAtomic ratios of O/Si | \n||
---|---|---|---|---|
\n | Si | \nO | \nC | \n|
As received SiC | \n19.05 | \n15.86 | \n65.09 | \n0.83 | \n
Colloidal | \n20.91 | \n33.64 | \n45.45 | \n1.60 | \n
Areosil 80 nm | \n23.59 19.82 | \n34.51 37.28 | \n41.35 42.90 | \n1.46 1.88 | \n
Needle shaped | \n25.66 | \n30.97 | \n43.37 | \n1.20 | \n
Surface chemical composition of neat SiC and coated nanoparticles.
\nFigures 6–9 depict the deconvoluted XPS spectra for peaks Si 2p, C 1s, and O 1s of the coated samples of colloidal, areosil, needle shaped and 80 nm nanoparticles. For each of the nanoparticles samples made using high intensity ultrasound irradiation, there were noticeable chemical shifts in peak observed indicating the coating of SiC onto SiO2 nanoparticles that took place. This was further confirmed from the elemental concentration at the surface. These spectra could be separated into two or three peaks based on the assumption that each peak consists of the Gaussian/Lorentzian sum function. The Si(2p) peak was separated into the Si▬Si, Si▬C, and SiOx peaks, and the C(1s) peak was decomposed into the C▬Si, C▬C, C▬O▬H, and C═O peaks [34, 35, 36, 37, 38, 39]. The energy positions of these peaks are listed in Table 3. The separation of the elements is not sufficient to precisely obtain the fraction of the bond. Therefore, as a rough estimation, the fraction of the bond was obtained from the ratio of the area of each peak [40]. The FWHM of Si▬Si and Si▬C are 2.13 and 1.38 eV, respectively. The FWHM of C▬C and C═C are 2.1 and 1.2 eV, respectively. The ratio between C▬C and C═C bond concentration is 10.1.
\nBond | \nBinding energy (eV) | \n
---|---|
Si▬Si | \n99.2 | \n
Si▬C | \n100.5 | \n
O▬Si▬C | \n101.8 | \n
SiOx\n | \n103.2 | \n
C▬Si | \n283.2 | \n
C▬C | \n284.6 | \n
C▬O▬H | \n286.4 | \n
C═O | \n288.4 | \n
Binding energy of different bonds.
Deconvoluted XPS spectrum of SiC/SiO2 (colloidal) for Si 2p peak and C 1s.
The deconvoluted XPS spectrum of SiC/SiO2 (Colloidal) for Si 2p peak and C 1s is shown in Figure 5. Similar results were obtained such as, the BE of 103.35, 99.99, and 97.91 eV that were associated with SiOx, Si▬C, and Si▬Si bonding, respectively, for Si 2p. Fitted curve for C 1s also showed similar results of C▬C and C▬Si bonding occurring. The O 1s emission was also found at BE of 532.55 eV. The surface chemical composition of Si, O and C obtained from CasaXPS were 20.91, 33.64 and 45.45, respectively.
\nThe deconvoluted XPS spectrum of SiC/SiO2 (Areosil) for Si 2p peak and C 1s is shown in Figure 7. The BE was found to be 103.48 and 100.089 eV for Si 2p which are associated with SiOx bonding and Si▬C bonding, respectively. Whereas, fitted curve for C 1s at 284.76 and 282.88 eV of BE was indicating the C▬C and C▬Si bonding. The O 1s emission was found at BE of 532.55 eV, and the surface chemical composition of Si, O, and C obtained from CasaXPS were 23.59, 34.51, and 41.35%, respectively. There was evident of small amounts of Na 1s present that accounted for the remaining 0.56% of the chemical composition. This was believed to be the result of surface or apparatus contamination.
\nDeconvoluted XPS spectrum of SiC/SiO2 (Areosil) for (a) Si 2p peak and (b) C 1s.
\nFigure 8 shows the deconvoluted XPS spectrum of SiC/SiO2 (needle shape) for Si 2p peak and C 1s. The BE was found to be associated with Si▬C bonding at 100.61 eV, Si▬Si at 98.35 and 103.74 eV related with Si▬O bonding, respectively, for Si 2p. Fitted curve for C 1s was also obtained at 284.46 and 283.02 eV of BE was indicating the C▬C and the Si▬C bonding. In addition to these, the O 1s emission was also found at BE of 532.55 eV. The surface chemical composition of Si, O, and C obtained from CasaXPS were 25.66, 30.97, and 43.37%, respectively.
\nDeconvoluted XPS spectrum of SiC/SiO2 (needle shape) for (a) Si 2p peak and (b) C 1s.
\nFigure 9 depicts the deconvoluted XPS spectrum of SiC/SiO2 (80 nm) for Si 2p peak and C 1s. The BE was found to be associated with Si▬C bonding at 100.41 and 103.84 eV related with Si▬O bonding, respectively, for Si 2p. On the other hand, fitted curve for C 1s at 284.76 and 282.28 eV of BE was indicating the C▬C and the Si▬C bonding. In addition to these, the O 1s emission was found at BE of 532.55 eV. The surface chemical composition of Si, O, and C obtained from CasaXPS was 19.82, 37.28 and 42.90 respectively.
\nDeconvoluted XPS spectra of SiC/SiO2 (80 nm) for (a) Si 2p and (b) C 1s.
The observed shift in the Si 2p peak between the oxide and the carbide is consistent with the expected change in oxidation state. Additional information on the interface was obtained from the C 1s photoelectron spectrum of the nominally bare SiC, far from the interface as shown in Figure 10. The narrow second highest energy peak is the expected C 1s signal from bulk SiC [41]. From the observed chemical shifts, we can determine the ionic state of a particular species. Although the incident X-rays penetrate deep into the sample, only electrons emitted from a thin surface layer are detected. The electron escape depth for Si, C, and O ranges from 2.0 to 2.5 nm [42].
\nXPS overlay of O 1s binding energy for SiC and the coated nanoparticles.
Differential scanning calolimetry (DSC) is a thermoanalytical technique by which the energy absorbed or emitted by the material as a function of temperature or time is measured. In present case, we have studied the extruded-polymer nanocomposites to determine the thermal transitions such as the melting (Tm) of a crystalline polymer as shown in Figure 11. The DSC data are presented in Table 4.
\nDSC melting curve of neat PP and nanocomposites.
The curve shapes of the neat material and nanocomposites are very similar, with only slight differences in the leading edge of the melt peak, indicating that the neat structure has little effect on the overall phase structure of the material. Above the melting temperature of about 160°C, the polymer is subject to a thermal degradation that is both dependent on time and on temperature. Adding nanoparticles allow the start of the degradation process to shift toward higher temperatures. The increase of the melting temperature of neat PP to PP + SiC was 161.43–166.12°C. Correlation has also been drawn between orientation (crystal perfection) and the DSC melt peak temperature [43].
\nThe crystallization peak temperatures are shown below in Figure 11; they follow the same order as the melt peak temperatures, with the neat pp material being more easily crystallizable. Preliminary isothermal crystallization studies at 116°C of neat polypropylene also show a similar trend. A decrease in the crystallization temperature after introduction of the filler indicates that a higher undercooling of the melt is necessary for the crystallization to occur. Such behavior may be the result of the strong influence of the SiC/SiO2 nanoparticles on the chain dynamics (lower chain mobility). It has been shown that the crystallization rate increases as both molecular weight and molecular weight distribution increase [44].
\nSeveral authors have seen multiple melting peaks in polypropylene, and there is the suggestion of multiple crystalline forms in the polypropylene [33, 44, 45]. It is alternatively suggested that the low temperature melting is caused by a less perfect crystalline order and not from different crystal phases [46]. With very sharp crystallization peaks, it is likely that the low temperature phase is induced at the crystallization temperature. Similar phenomena have been observed for isothermal crystallization [47] and this probably explains the difference in peak temperature between the nanocomposites. It is also plausible that the different polymer fractions do not co-crystallize simultaneously, and that the lower temperature melts is due to morphological effects. It is possible that the higher melt temperature of neat PP implies the molecular weight of the nanocomposites is greater than the neat PP (Table 4).
\nSample | \nMelting temperatures (°C) | \nCrystallization temperatures (°C) | \n
---|---|---|
Pure PP | \n161.43 | \n113.72 | \n
Neat areosil | \n165.48 | \n111.12 | \n
Neat 80 nm | \n163.16 | \n112.83 | \n
Neat needle shape | \n165.60 | \n111.31 | \n
PP + SiC | \n161.51 | \n116.80 | \n
Coated areosil | \n166.12 | \n113.20 | \n
Coated colloidal | \n162.84 | \n113.54 | \n
Coated 80 nm | \n163.70 | \n111.72 | \n
DSC melting and crystallization temperature chart.
The applications of TGA are to determine the absorbed moisture content, residual solvent levels, the amount of inorganic filler in a polymer, and in this case the degradation characteristics of the coated nanocomposites in terms of their induction time. The weight loss of a polymer as a function of temperature is commonly determined by this technique. Weight loss of a polymer due to thermal degradation is an irreversible process. Such thermal degradation is largely related to oxidation whereby the molecular bonds of a polymer are attacked by oxygen molecules. Figure 12 is the TGA graph of extruded neat silicon carbide coating with polypropylene and extruded samples of coated nanoparticles with polypropylene. The TGA data are presented in Table 5.
\nTGA curves of neat and SiC/SiO2 reinforced polypropylene nanocomposite.
Sample | \nTd (°C) | \nT50 (°C) | \n% Temperature increase | \n
---|---|---|---|
Pure PP | \n369.78 | \n436.06 | \n— | \n
Neat areosil | \n452.94 | \n488.59 | \n12.0 | \n
Neat 80 nm | \n469.68 | \n496.34 | \n13.8 | \n
Neat needle shape | \n464.94 | \n493.48 | \n13.1 | \n
PP + SiC | \n453.67 | \n483.60 | \n10.9 | \n
Coated areosil | \n454.06 | \n486.11 | \n11.4 | \n
Coated colloidal | \n446.79 | \n487.50 | \n11.7 | \n
Coated 80 nm | \n447.71 | \n482.39 | \n10.6 | \n
Parameters obtained from TGA curves.
In the present study, TGA results show that 50% of the total weight loss is considered as the structural destabilization point of the system. It is a common practice to consider 50% weight loss as an indicator for structural destabilization. From Figure 12, it is evident that the neat sample is stable up to 436.06 °C, whereas the coated nanocomposites minimum stabilization temperature is at 482.39°C which is a 10.6% increase. The maximum temperature increase was 13.8% and stabilization occurred at 496.34°C for the neat 80 nm sample. The reason for this increase in the thermal stability is due to the increase in cross-linking of the coated nanoparticles in the presence of polypropylene and having minimum particle to particle interaction.
\nThis may be due to the presence of silicon carbide nanoparticles which are high heat absorbing materials compared to neat polypropylene, which can be the reason for having such a positive impact on improving the decomposition temperature. One can also assume that the nanoparticles were well dispersed and were not acting as impurities in agglomerated form due to the increase. Another probable reason for the observed behavior could be the lower mobility of the polymer chains due to strong interaction with the nanofiller. Thermal degradation of polypropylene begins with formation of the free radicals, which further induce chain fragmentation processes [48]. Volatile oligomers that are formed which are responsible for the mass loss will be partially prevented which results in the whole degradation process to shift towards a higher temperature.
\nThe flexure test method measures behavior of materials subjected to simple beam loading. It produces tensile stress in the convex side of the specimen and compression stress in the concave side which creates an area of shear stress along the midline.
\nFlexure stress-strain curves for neat polypropylene and the nanocomposites are shown in Figure 13. The flexural test data are presented in Table 6. From the graph, it is evident that flexural strength and modulus slightly increases with the addition of coated SiC/SiO2 nanofillers with respect to the neat polymer. In the table, we see that coated colloidal contributed the maximum percent change in stiffness at 40.5%, while the coated 80 nm contributed to a maximum strength percent change at 24.6%, and the greatest toughness percent change which was at 92.4%. Although these were the highest values observed, it is still evident that overall, all of the samples performed greater than the neat PP sample.
\nStress-strain curve from flexure results.
The reason for such change in stiffness of the matrix is due to ultrasound irradiation which enhances the homogeneity. The ultrasound irradiation helps in molecular mixing of these components together and the formation of coated reactive particles which ultimately leads to increase the cross-linking in the polymer when mixed. The decrease in mobility of the cross linking in polymer gives better mechanical properties with an optimum amount of nanofiller addition. Surface area also played an important role in the significant increase in that the spherical spatial distribution and low weight ratio of the nanofillers enhance the homogeneity of the reaction. The nanocomposites exhibit ductile fracture and the elongation at break increased with the increase of the nanoparticle content (Table 6).
\nSample | \nStrength (MPa) | \n% Strength change | \nModulus | \n% Modulus change | \nStrain (%) | \n% Increase in toughness | \n
---|---|---|---|---|---|---|
Pure PP | \n33.97 | \n— | \n1.16 | \n— | \n7.09 | \n— | \n
Neat areosil | \n35.82 | \n5.4 | \n1.31 | \n12.9 | \n6.83 | \n13.2 | \n
Neat 80 nm | \n37.50 | \n10.3 | \n1.42 | \n22.4 | \n6.65 | \n22.4 | \n
Neat needle shape | \n39.76 | \n17.0 | \n1.48 | \n27.5 | \n6.61 | \n27.5 | \n
PP + SiC | \n38.88 | \n14.4 | \n1.45 | \n25 | \n6.50 | \n25 | \n
Coated areosil | \n39.26 | \n15.5 | \n1.49 | \n28.4 | \n6.29 | \n30.1 | \n
Coated colloidal | \n41.65 | \n22.6 | \n1.63 | \n40.5 | \n6.48 | \n41.5 | \n
Coated 80 nm | \n42.33 | \n24.6 | \n1.28 | \n10.3 | \n7.29 | \n92.4 | \n
Mechanical properties from flexure test.
The samples were prepared using high intensity ultrasound irradiation to coat SiC onto SiO2 nanoparticles. This process has been introduced as an efficient way to disperse SiC onto SiO2 nanoparticles, and by extruding these samples with polypropylene, it increases its mechanical properties. XRD analysis confirmed that the samples were crystalline with an amorphous background present. The TEM analysis revealed that the SiC nanoparticles were uniformly dispersed over the entire surface of the SiO2 nanoparticles. It also indicated a minor growth in the size of the nanoparticles after ultrasonic irradiation. XPS spectrographs revealed the chemical composites found in the samples. It also verified the surface coating through the shifts in binding energies. The crystallization of the polypropylene polymer matrix was also affected by the presence of the coated nanoparticles. DSC testing indicated that the crystallization and the melting temperatures increased with increasing filler content. Through DSC, it can be seen that by adding nanoparticles, it allows the start of the degradation process to shift toward higher temperatures. The increase of the melting temperature of neat PP to PP + SiC was 161.43–166.12°C. A decrease in the crystallization temperature after introduction of the filler indicates that a higher undercooling of the melt is necessary for the crystallization to occur. The TGA data showed that the neat sample is stable up to 436.06°C, whereas the coated nanocomposites minimum stabilization temperature is at 482.39°C which is a 10.6% increase. The maximum temperature increase was 13.8% and stabilization occurred at 496.34°C for the neat 80 nm sample. The coated nanocomposites had profound effects on the PP properties. The flexure test results showed that the flexural strength and modulus slightly increases with the addition of coated SiC/SiO2 nanofillers with respect to the neat polymer.
\nThe authors acknowledge the financial support of NSF-RISE # 1459007, NSF-CREST#1735971 and NSF-MRI-1531934 grants.
\nThe authors declare no conflict of interest.
.
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