Electric/thermal parameters of the most relevant polymer nanocomposites with carbon nanoparticles.
\\n\\n
More than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\\n\\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\\n\\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\\n\\nAdditionally, each book published by IntechOpen contains original content and research findings.
\\n\\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\\n\\n\\n\\n
\\n"}]',published:!0,mainMedia:{caption:"IntechOpen Maintains",originalUrl:"/media/original/113"}},components:[{type:"htmlEditorComponent",content:'
Simba Information has released its Open Access Book Publishing 2020 - 2024 report and has again identified IntechOpen as the world’s largest Open Access book publisher by title count.
\n\nSimba Information is a leading provider for market intelligence and forecasts in the media and publishing industry. The report, published every year, provides an overview and financial outlook for the global professional e-book publishing market.
\n\nIntechOpen, De Gruyter, and Frontiers are the largest OA book publishers by title count, with IntechOpen coming in at first place with 5,101 OA books published, a good 1,782 titles ahead of the nearest competitor.
\n\nSince the first Open Access Book Publishing report published in 2016, IntechOpen has held the top stop each year.
\n\n\n\nMore than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\n\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\n\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\n\nAdditionally, each book published by IntechOpen contains original content and research findings.
\n\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\n\n\n\n
\n'}],latestNews:[{slug:"webinar-introduction-to-open-science-wednesday-18-may-1-pm-cest-20220518",title:"Webinar: Introduction to Open Science | Wednesday 18 May, 1 PM CEST"},{slug:"step-in-the-right-direction-intechopen-launches-a-portfolio-of-open-science-journals-20220414",title:"Step in the Right Direction: IntechOpen Launches a Portfolio of Open Science Journals"},{slug:"let-s-meet-at-london-book-fair-5-7-april-2022-olympia-london-20220321",title:"Let’s meet at London Book Fair, 5-7 April 2022, Olympia London"},{slug:"50-books-published-as-part-of-intechopen-and-knowledge-unlatched-ku-collaboration-20220316",title:"50 Books published as part of IntechOpen and Knowledge Unlatched (KU) Collaboration"},{slug:"intechopen-joins-the-united-nations-sustainable-development-goals-publishers-compact-20221702",title:"IntechOpen joins the United Nations Sustainable Development Goals Publishers Compact"},{slug:"intechopen-signs-exclusive-representation-agreement-with-lsr-libros-servicios-y-representaciones-s-a-de-c-v-20211123",title:"IntechOpen Signs Exclusive Representation Agreement with LSR Libros Servicios y Representaciones S.A. de C.V"},{slug:"intechopen-expands-partnership-with-research4life-20211110",title:"IntechOpen Expands Partnership with Research4Life"},{slug:"introducing-intechopen-book-series-a-new-publishing-format-for-oa-books-20210915",title:"Introducing IntechOpen Book Series - A New Publishing Format for OA Books"}]},book:{item:{type:"book",id:"7198",leadTitle:null,fullTitle:"Propulsion Systems",title:"Propulsion Systems",subtitle:null,reviewType:"peer-reviewed",abstract:"The transport sector is one of the most valuable sectors in the world. It represents the large oil consumers but still relies mainly on fossil fuels. Since the world trend in fossil fuel use is expected to increase further, a more sustainable transportation system is unavoidable to cope with emerging economic and social issues, such as massive energy consumption and emissions of pollutant gases. In this regard, this book provides an overview of some recent and promising technological advancements in propulsion systems, ranging from on-board components to different propulsion system architectures. In particular, the book aims at giving a brief but significant insight into propulsion system design and architecture, by covering different topics and application fields (road, marine, and aerospace).",isbn:"978-1-83962-280-9",printIsbn:"978-1-83962-279-3",pdfIsbn:"978-1-83962-281-6",doi:"10.5772/intechopen.73998",price:119,priceEur:129,priceUsd:155,slug:"propulsion-systems",numberOfPages:152,isOpenForSubmission:!1,isInWos:1,isInBkci:!1,hash:"fd56f1620b0b201a3de0cd3f7e04d15c",bookSignature:"Alessandro Serpi and Mario Porru",publishedDate:"October 7th 2019",coverURL:"https://cdn.intechopen.com/books/images_new/7198.jpg",numberOfDownloads:10365,numberOfWosCitations:6,numberOfCrossrefCitations:12,numberOfCrossrefCitationsByBook:0,numberOfDimensionsCitations:20,numberOfDimensionsCitationsByBook:0,hasAltmetrics:1,numberOfTotalCitations:38,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"June 19th 2018",dateEndSecondStepPublish:"August 29th 2018",dateEndThirdStepPublish:"October 28th 2018",dateEndFourthStepPublish:"January 16th 2019",dateEndFifthStepPublish:"March 17th 2019",currentStepOfPublishingProcess:5,indexedIn:"1,2,3,4,5,6,7",editedByType:"Edited by",kuFlag:!1,featuredMarkup:null,editors:[{id:"217145",title:"Dr.",name:"Alessandro",middleName:null,surname:"Serpi",slug:"alessandro-serpi",fullName:"Alessandro Serpi",profilePictureURL:"https://mts.intechopen.com/storage/users/217145/images/system/217145.png",biography:"Alessandro Serpi got the master Degree in Electrical Engineering and the PhD in Industrial Engineering at the University of Cagliari (UNICA) in 2004 and 2009 respectively. He then did research on Power Electronics, Electrical Machines and Drives at the Department of Electrical and Electronic Engineering (DIEE) of UNICA as a post-doc researcher. Since November 6, 2015, Alessandro Serpi has been an Assistant Professor at DIEE. His research activity currently concerns the development and implementation of optimal/predictive control algorithms for electrical drives and energy storage systems. Alessandro Serpi is a co-author of 75 scientific publications in international journals and conference proceedings and of two book chapters. He is the proposing associate of “NEPSY” (Novel Electric Propulsion System), an academic spin-off of UNICA that was setup in August 2017.",institutionString:"University of Cagliari",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"1",institution:{name:"University of Cagliari",institutionURL:null,country:{name:"Italy"}}}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,coeditorOne:{id:"217148",title:"Dr.",name:"Mario",middleName:null,surname:"Porru",slug:"mario-porru",fullName:"Mario Porru",profilePictureURL:"https://mts.intechopen.com/storage/users/217148/images/system/217148.png",biography:"Mario Porru got the bachelor and master degrees in Electrical Engineering and the Ph.D. degree in electronic and computer engineering from the University of Cagliari (UNICA), Italy, in 2009, 2011, and 2015, respectively. From 2015 to 2018 he was a post-doc researcher with the Department of Electrical and Electronic Engineering (DIEE) of UNICA. Since April 2018 he is an Assistant Professor on Power Electronics, Electrical Machines and Drives at the same institution. His research activity focuses on management and control of energy storage systems, and highly integrated electric propulsion systems. He is a co-author of 27 papers published in international conference proceedings and journals and of a book chapter. Mario Porru is a co-founder of NEPSY (Novel Electric Propulsion Systems), a spin-off company of UNICA.",institutionString:"University of Cagliari",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"0",institution:null},coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"124",title:"Vehicle Engineering",slug:"vehicle-engineering"}],chapters:[{id:"64509",title:"Options and Evaluations on Propulsion Systems of LNG Carriers",doi:"10.5772/intechopen.82154",slug:"options-and-evaluations-on-propulsion-systems-of-lng-carriers",totalDownloads:4207,totalCrossrefCites:5,totalDimensionsCites:11,hasAltmetrics:1,abstract:"The LNG carriers are undergoing a period of rapid and profound change, with much larger size ships and novel propulsion systems emerging for fulfilling the market trends of LNG shipping industry. There are various proposed propulsion solutions for LNG carriers, ranging from the conventional steam turbine and dual fuel diesel electric propulsion, until more innovative ideas such as slow speed dual fuel diesel engine, combined gas turbine electric & steam system, and hybrid propulsion based on steam turbine and gas engine. Since propulsion system significantly influenced the ship’s capital, emission regulation compliance and navigation safety, the selection of a proper propulsion option with technical feasibility and economic viability for LNG carriers is currently a major concern from the shipping industry and thus must be comprehensively assessed. In this context, this chapter investigated the main characteristics of these propulsion options in terms of BOG treatment, fuel consumption, emission standards compliance, and plant reliability. Furthermore, comparisons among different propulsion system were also carried out and related evaluation was presented.",signatures:"Tu Huan, Fan Hongjun, Lei Wei and Zhou Guoqiang",downloadPdfUrl:"/chapter/pdf-download/64509",previewPdfUrl:"/chapter/pdf-preview/64509",authors:[{id:"265951",title:"Mr.",name:"Huan",surname:"Tu",slug:"huan-tu",fullName:"Huan Tu"}],corrections:null},{id:"65271",title:"Overview of Main Electric Subsystems of Zero-Emission Vehicles",doi:"10.5772/intechopen.82876",slug:"overview-of-main-electric-subsystems-of-zero-emission-vehicles",totalDownloads:1523,totalCrossrefCites:1,totalDimensionsCites:1,hasAltmetrics:1,abstract:"The rapid growth of the electric vehicle market has stimulated the attention of power electronics and electric machine experts in order to find increasingly efficient solutions to the demands of this application. The constraints of space, weight, reliability, performance, and autonomy for the power train of the electric vehicle (EV) have increased the attention of scientific research in order to find more and more appropriate technological solutions. In this chapter, it proposes a focus on the main subsystems that make a zero-emission vehicle (ZEV), examining current features and topological configurations proposed in the literature. This analysis is preliminary to the various electric vehicle architectures proposed in the final paragraph. In particular, the electric drive represents the core of the electric vehicle propulsion. It is realized by different subsystems that have a single mission: ensure the requested power/energy based on the operating condition. Particular attention will be devoted to power subsystems, which are the fundamental elements to improving the performance of the ZEV.",signatures:"Adolfo Dannier",downloadPdfUrl:"/chapter/pdf-download/65271",previewPdfUrl:"/chapter/pdf-preview/65271",authors:[{id:"272014",title:"Ph.D.",name:"Adolfo",surname:"Dannier",slug:"adolfo-dannier",fullName:"Adolfo Dannier"}],corrections:null},{id:"65736",title:"Wetland Monitoring Using Unmanned Aerial Vehicles with Electrical Distributed Propulsion Systems",doi:"10.5772/intechopen.84402",slug:"wetland-monitoring-using-unmanned-aerial-vehicles-with-electrical-distributed-propulsion-systems",totalDownloads:1127,totalCrossrefCites:5,totalDimensionsCites:6,hasAltmetrics:0,abstract:"The inspection of wetlands in the Ecuadorian highlands has gained importance due to the environmental issues linked to the growth of human activities and the expansion of the agricultural and livestock frontiers. In this sense, unmanned aerial vehicles (UAVs) have been amply used in monitoring activities such as the supervision of threatened ecosystems, where cyclic measurements and high-resolution imagery are needed. However, the harsh operating conditions in the Andean highlands and sensitive ecosystem restrictions demand efficient propulsion configurations with low environmental impact. Electrical distributed propulsion (EDP) systems have surged as a forefront alternative since they offer benefits in both the propulsive and aerodynamic performance of fixed-wing UAVs. In this chapter, an EDP system is sized for a design point at the Andean operating conditions. Thereafter, two propulsion configurations were established based on off-the-shelf components, and their performance was characterized through analytical approaches. These results highlight the trends in power consumption and performance when the number of propulsors is increased. A significant contribution of this work is to exhibit important patterns in the performance of electric propulsion by using commercial components, and to set the operating limitations that can be further explored for analogous configurations in larger UAVs.",signatures:"Esteban Valencia, Víctor Alulema and Darío Rodríguez",downloadPdfUrl:"/chapter/pdf-download/65736",previewPdfUrl:"/chapter/pdf-preview/65736",authors:[{id:"198406",title:"Ph.D.",name:"Esteban",surname:"Valencia",slug:"esteban-valencia",fullName:"Esteban Valencia"},{id:"287319",title:"BSc.",name:"Victor",surname:"Alulema",slug:"victor-alulema",fullName:"Victor Alulema"},{id:"287321",title:"BSc.",name:"Dario",surname:"Rodriguez",slug:"dario-rodriguez",fullName:"Dario Rodriguez"}],corrections:null},{id:"64539",title:"Beamed Launch Propulsion",doi:"10.5772/intechopen.82236",slug:"beamed-launch-propulsion",totalDownloads:1693,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:1,abstract:"An advanced concept of launch system from ground to orbit, called laser launch system, has been discussed. As a 100-kW-class fiber laser has been developed today, the laser propulsion is now a realistic option for launching microsatellites frequently at very low cost. In this chapter, we shall discuss several unresolved technical problems such as propulsion design and laser beam transmission through atmosphere. It is proved theoretically that high specific impulse higher than 900 seconds is possible in a new conceptual design. On the other hand, the laser beam may be suffered by the atmospheric turbulence when the launch vehicle reaches at altitude higher than 10 km.",signatures:"Koichi Mori",downloadPdfUrl:"/chapter/pdf-download/64539",previewPdfUrl:"/chapter/pdf-preview/64539",authors:[{id:"265661",title:"Dr.",name:"Koichi",surname:"Mori",slug:"koichi-mori",fullName:"Koichi Mori"}],corrections:null},{id:"64914",title:"Hall Thruster Erosion",doi:"10.5772/intechopen.82654",slug:"hall-thruster-erosion",totalDownloads:812,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:"Hall thruster (HT) is one of the thrusters that are systematically applied in space. If to compare HT with plasma ion thrusters, it has lower lifetime and specific impulse. HT has a set of advantages, and that is why interest to this plasma thruster is high. It has relatively simple design and technology of production. HT does not require a complex power supply unit, and it is very important for spacecraft. Propulsion system on the base of HT has lower mass, simpler technology, and less time of production. One of the main HT characteristics that require improvement is the lifetime of thruster. As it is known, one of the main factors that decrease thruster lifetime is the wear of discharge chamber (DCh). With the analysis of demands to HT, it is understandable that the required lifetime is more than 10 years. So the question about lifetime of the HT is still open. This chapter presents the overview of the thruster elements lifetimes and the overview of methods of thruster erosion investigation. It shows advantages and disadvantages of optical methods of DCh erosion rate investigation. Chapter presents modified method of optical investigation. The results of HT research under various modes of operation and results of tests with different ceramic are presented.",signatures:"Andrey Vitalievich Loyan and Alona Nikolaevna Khaustova",downloadPdfUrl:"/chapter/pdf-download/64914",previewPdfUrl:"/chapter/pdf-preview/64914",authors:[{id:"267092",title:"Dr.",name:"Andriy",surname:"Loyan",slug:"andriy-loyan",fullName:"Andriy Loyan"},{id:"267096",title:"Dr.",name:"Alona",surname:"Khaustova",slug:"alona-khaustova",fullName:"Alona Khaustova"}],corrections:null},{id:"68530",title:"Biological Propulsion Systems for Ships and Underwater Vehicles",doi:"10.5772/intechopen.82830",slug:"biological-propulsion-systems-for-ships-and-underwater-vehicles",totalDownloads:1004,totalCrossrefCites:1,totalDimensionsCites:2,hasAltmetrics:1,abstract:"Regulations and performance requirements related to technology development on all modes of transport vehicles for reduced pollution and environmental impact have become more stringent. Greening of transport system has been recognized as an important factor concerning global warming and climate change. Thus environment-friendly technical solutions offering a reduction of noxious exhaust gases are in demand. Aquatic animals have good swimming and maneuvering capabilities and these observations have motivated research on fish-like propulsion for marine vehicles. The fish fin movements, used by fish for their locomotion and positioning, are being replicated by researchers as flapping foils to mimic the biological system. Studies show that flapping foil propulsion systems are generally more efficient than a conventional screw propeller, which suffers efficiency losses due to wake. The flapping foil propulsors usually do not cavitate and have less wake velocity variation. These aspects result in the reduction of noise and vibration. The present study will cover an overview of aquatic propulsion systems, numerical simulations of flapping foils and ship model self-propulsion experiments performed using flapping foil system, particle image velocimetry (PIV), and digital fluoroscopy studies conducted on fish locomotion. Studies performed on underwater and surface vehicles fitted with flapping fins will also be presented.",signatures:"Naga Praveen Babu Mannam and P. Krishnankutty",downloadPdfUrl:"/chapter/pdf-download/68530",previewPdfUrl:"/chapter/pdf-preview/68530",authors:[{id:"264509",title:"Dr.",name:"Naga Praveen Babu",surname:"Mannam",slug:"naga-praveen-babu-mannam",fullName:"Naga Praveen Babu Mannam"},{id:"264512",title:"Prof.",name:"P.",surname:"Krishnankutty",slug:"p.-krishnankutty",fullName:"P. 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Patients presenting with hair loss (alopecia) is a very common problem and is often a cause of great concern for cosmetic and psychological reasons and this has several causes; as it may be an important sign of systemic disease.
Alopecia can be either scarring or non-scarring. Non-scarring alopecias tend to have preserved follicular ostia, with no clinically visible inflammation in most presentations, although histologic inflammation may be present. The common types of non-scarring alopecias are androgenic alopecia, telogen effluvium, alopecia areata, trichotillomania and traction alopecia. Scarring alopecias, also known as cicatricial alopecia, refers to a collection of hair loss disorders that have loss of follicular ostia, or atrophy, with permanent and irreversible destruction of hair follicles and their replacement with scar tissue. The histologic confirmation is the best method to confirm the presence of a fibrosing/scarring process with loss of hair follicles.
Scarring alopecias can be classified as lymphocytic (discoid lupus erythematosus (DLE), lichen planopilaris (LPP), central centrifugal cicatricial alopecia, pseudopelade of Brocq), neutrophilic (folliculitis decalvans, dissecting folliculitis), and mixed (acne keloidalis) entities [1].
Many alopecia types are biphasic. For example, androgenetic alopecia eventually results in loss of ostia and thus may appear like a scarring alopecia.
To establish the cause of the hair loss, one requires a history to identify known triggers, scalp examination, biochemical investigations and in many cases histology to identify the earliest stages of some types of alopecias esp scarring alopecia.
Scalp biopsies can be used to make or confirm a diagnosis of alopecia. Scalp biopsy is considered mandatory in all cases of scarring alopecia. The interpretation of the histopathological findings of primary scarring alopecias without known clinical history may be difficult and this is especially true if the biopsy specimen is inadequate.
In non-scarring type, it is not difficult to diagnose these disorders. However, scalp biopsy can be needed in few cases of:
Lack of identifiable triggers.
Severe hair loss (as in some cases of alopecia areata which does not present in a well defined bald area, but as severe hair loss (Fig 1).
Acute hair loss.
Telogen effluvium does not occur in an acute way after a known triggering factor.
Some cases of female androgenetic alopecia pattern; the clinical presentation may be similar to other types of non-scarring alopecias.
year old female patient presented with diffuse, acute severe hair loss and with localized patch of alopecia areata as it demonstrated by red arrow.
It is a crucial to determine the appropriate site of a scalp biopsy to have a correct diagnosis of alopecia, and this approach is different in scarring and non-scarring types. For a scarring process, the biopsy should be taken from the active border of hair loss where some hairs still remain and are more likely to display diagnostic findings. For non-scarring alopecias, the preferred site of biopsy is generally the border of a lesion (positive exclamation marks in alopecia areata), or from the site of a positive pull test in the setting of a diffuse alopecia. In the setting of evaluating a possible androgenic alopecia, two biopsies, one from the involved scalp (often vertex) and one from the uninvolved scalp (often occiput; serves as a positive control) may be beneficial.
The current gold-standard for a scalp biopsy specimen is the use of a 4-mm punch and must include subcutaneous fat to ensure sampling of the entire follicular unit and any anagen follicles; the specimen may be sectioned vertically or transversely [2]. Although a combination of the two may be optimal, the pathologist is frequently only provided with a single specimen.
Vertically-sectioned punch biopsy specimen is adequate for assessing alopecias associated with interface changes, lichenoid infiltrates, and subcutaneous pathology [3]. However, vertical sectioning will show only 10% of the follicles present in the specimen [4]because the hair follicles, which grow at an angle, cannot be visualized in their entirety in conventional vertical sections.
Vertical section of a scalp biopsy from a patient with DLE.
Horizontal sections are becoming the method of choice as they offer the advantage of evaluating large numbers of follicles simultaneously, determining hair density, location of inflammatory infiltrate and anagen to telogen ratio [5]. A transversely sectioned specimen will include all the hair follicles present in the biopsy, and in the same section. Although the clinical impression is very important in diagnosing alopecia, transversely sectioned biopsy specimens can greatly aid the diagnosis and management of patients with alopecia [6].
Transverse section from a scalp biopsy from a patient with DLE.
The histological findings in many forms of hair loss may be similar, and an accurate diagnosis of hair loss depends on distinguishing abnormal from normal follicular architecture. It is important to identify the normal hair follicle structure, the number, size and distribution of hair follicles within a biopsy specimen. Hematoxylin and eosin staining of the scalp biopsies is the usual satin in most of the cases of hair loss, but in some of the alopecias (such as DLE), immunofluorescence staining may be needed to add in diagnosis. In addition, the pathologist may use additional special stains to narrow a differential diagnosis or confirm an initial impression and one of these is immunohistochemistry which is dependent on the localization of antigens in tissue sections by the use of labeled antibody as specific reagents through antigen-antibody interactions that are visualized by a marker such as peroxidase.
Specimens are categorized as scarring or nonscarring alopecia, and further diagnostic criteria discussed herein assist the pathologist in making specific diagnoses of nonscarring and scarring alopecias.
Histologically, cicatricial alopecia is characterized by dermal scarring, along with absent or reduced hair follicles and reduced number of erector pili muscles. But taking skin biopsy from the active area will be more informative about the diagnosis.
This scarring alopecia may be secondary, and due to numerous etiologies (such as due to infectious causes (Fig 4), or primary, where the cause and pathogenesis are largely unknown, but the target is the hair follicle itself (such as DLE and LPP).
The discussion in following sections is about the primary type as the skin biopsy is more informative about the diagnosis.
Scarring alopecia in a child secondary to tinea capitis.
Lupus erythematosus is an autoimmune disease that can affect one or more internal organs as well as the skin. This disease is a clinical spectrum ranging from mildly affected patients with only localized skin disease to those at risk of dying from systemic manifestations. The skin involvement is among the most frequent symptoms; and is characterized by its natural history of relapsing and chronicity. The scalp (Fig 5) is a common area of involvement, and permanent alopecia may result with the following morphological features; sclero-atrophy, erythema, follicular hyperkeratosis, plugging and telangiectasia. The irreversible, scarring alopecia differs from the reversible non scarring alopecia that is seen in patients with systemic lupus erythematosus.
Scarring alopecia in DLE may mimic other types of scarring alopecia seen in some dermatoses, the most common differential diagnosis of this is lichen planopilaris (LPP) and the differentiation between them is possible by early clinical and histological changes. Both LPP and DLE show perifollicular erythema and keratotic follicular papules, but the distinctive clinical features of DLE of the scalp are the presence of erythema, scaling, telangiectasia, and mottled hyperpigmentation within the areas of scarring alopecia and the presence of hyperkeratotic papules in the central part of the bald area in DLE, while in LPP it presents at the margin of the alopecia patch [7].
Discoid lupus erythematosus of the scalp. The typical scaling is evident.
DLE is a scarring disease and so early treatment is needed to control existing cutaneous lesions and limit scaring and to prevent the development of the disease. Patients with DLE lesions should have regular clinical evaluation accompanied by simple laboratory studies to evaluate the possible progression from the primary cutaneous disorder to the disorder accompanied by systemic involvement. Therapy begins with general measures such as the use of sun-protective measures, including sunscreens, protective clothing and medical therapy includes corticosteroids (topical or intralesional) and antimalarials.
Routine histologic examination of lesional skin from CLE patients is necessary, as the diagnosis of CLE generally requires clinicopathologic correlation and the distinction between different types of CLE based on histological findings without clinical correlation is difficult; all forms of CLE are similar histologically in broad terms. Histopathological features (Fig 6) include pilosebaceous atrophy, hyperkeratosis, parakeratosis, basement membrane thickening, subepidermal oedema and vasodilatation. A perivascular and peri-appendageal superficial and deep lymphoid cell infiltrate with plasma cells are other histolopathological findings.
DLE pathology. Note the hyperkeratosis, basal cell degeneration and heavy inflammatory infiltrate.
Direct immunofluorescence (DIF) of lesional skin in CLE is an adjunctive test; it helps to confirm the diagnosis when the routine histological findings are equivocal. The test is positive only in some of lesional skin biopsies; so light microscopy should be carried out before DIF. For DIF, the optimal lesion of LE should be an established, erythematosus lesion, and of at least 6-8 weeks in duration. The most suggestive findings are the presence of multiple immunoreactants typically IgG and IgM, in a special pattern (bright in intensity, continuous, perifollicular, and granular) [8]. Sometimes complement components may be present including C3b and C1q. Scalp lesions have been reported to show the highest frequency of the DIF test (83 %), the immunoreactants deposits occur around hair follicles, an important feature not seen in other types of scarring alopecia.
Using immunohistochemistry [9], there were significant alterations in the basement membrane zone (BMZ) in patients with active DLE and this explain the previous histological findings of thickened BMZ in DLE. There was an increase in the expression of the anchoring fibril and collagen component antigens in the BMZ with gross thickening and protrusion into the dermis in active DLE lesions (Fig 7).
Anti-type IV collagen staining in DLE with an exaggerated expression as demonstrated by thickness of the basement membrane and protrusions.
LPP is a rare type of lichen planus which characteristically affects the scalp (Figure 8) with perifollicular erythema, keratotic follicular spines and with patchy or diffuse hair loss which may result in scarring alopecia as its end stage. Scalp lesions can be associated with characteristic flat topped violaceous papules of lichen planus (LP) on the limbs in 50 % of cases [10]. LPP of the scalp is a scarring disease and it is difficult to treat comparing to the glabrous LP and this has major psychological consequences for the affected patients. The therapeutic management often is quite challenging, as relapses are common after local or systemic treatments. The recommended treatments are ultrapotent topical or intralesional injections of corticosteroid. Some cases may need systemic treatment including oral corticotherapy and cyclosporine.
LPP of the scalp.
Histologically (Fig 9) has been reported to show two different patterns [11], each pattern characterized by the presence of specific histological features that reflects the specific stage of the progression of the disease. In the first pattern, hair follicles and the perifollicular dermis were mainly involved in the pathologic process, with no involvement of the interfollicular structures. In the second pattern, the pathologic changes extended to the interfollicular epidermis and the papillary dermis.
LPP pathology. The inflammation is mainly perifollicular with some involvement of the basal cell layers which also show basal cell degeneration.
Direct immunofluorescence highlights the presence of colloid bodies in the peri-infundibular area staining with IgM (less frequently with IgG, IgA and C3).
By immunohistochemistry staining [12], there is a significant alteration in the basement membrane structure in lesions of LPP which could differentiate it from active lesions of scalp DLE lesions.
Anti-type IV collagen staining in LPP. Interrupted expression of type IV collagen in an affected hair follicle in an LPP lesion with projections into the underlying dermis, with the adjacent epidermis showing normal expression of the collagen
The diagnosis of this type of alopecia is usually based on a thorough history and a focused physical examination. In some patients, punch biopsy may be necessary if the cause of hair loss is unclear as has been described previously. The focus in the following discussion will be on alopecia areata and androgenetic alopecia (the skin biopsies will be needed in some of cases).
Alopecia areata (Fig 11) is one form of non-scarring alopecia characterize by patchy hair loss of autoimmune origin. It usually presents as a single or multiple confluent patches of non-scarring alopecia. Spontaneous regression of the disease is common in this disease and the hair may grow back if the affected region is small. Topical treatment is effective including corticosteroids clobetasol or fluocinonide, corticosteroid injections, or cream, steroid injections, topical minoxidil, irritants (anthralin or topical coal tar), and topical immunotherapy. Oral corticosteroids decrease the hair loss, but only for the period during which they are taken.
Diagnostic pathological findings (Fig 12) are more prominent in this type of alopecia which characterize by peribulbar lymphocytic inflammation which is usually considered to be an essential finding in establishing the diagnosis [13]. The lymphocytic
infiltrate is rich in helper T cells, which are considered to be evidence of an autoimmune process. Despite this, it may be absent in many scalp biopsy specimens. In the acute stage; a moderate to dense inflammatory cell infiltrate (mainly lymphocytes and langerhans cells) [14] develops around anagen hair and this leads finally to anagen arrest and inhibition which weakens the lowest portion of the
hair shaft. Using follicular counts [15] related to the stage of disease is a useful way to establish the histologic features of alopecia areata in scalp biopsy specimens taken from different types of alopecia areata; alopecia areata should be suspected when high percentages of telogen hairs are present, even in the absence of a peribulbar infiltrate [15].
Alopecia areata in a child presented with diffuse hair loss.
Skin biopsy from a patient with alopecia areata demonstrating perifollicular lymphocytic infiltrate.
Androgenic alopecia is the most common type of hair loss. Clinically, it is a patterned alopecia, in that it is characterized by bitemporal recession and vertex balding in men, and in women (female pattern hair loss) by diffuse hair thinning of the crown with an intact frontal hairline. Histopathologically, the use of transverse sections is the most valuable method to reach a diagnosis [16], as all the hair follicles can be visualized.
The terminal (T) to vellus (v) ratio is T: V= less than 4:14. Normal scalp ratio is T: V= 7:1). A ratio of T: V= 3: 1 or less is considered to be diagnostic [16], [17].
From the discovery of cylindrical nanometric structures composed of one or several layers of carbon atoms similar to graphite by Iijima in 1991 [1], the scientific community embarked on a fascinating multidisciplinary career in the study, synthesis, characterization, and possible applications of these new carbon nanostructures, excited by the unusual combination of properties that these nanomaterials possess, among which the conduction of electricity and heat, low density, high mechanical resistance and morphology stand out. These nanoparticles have diameters in the range of 1 to 100 nm, lengths of 10 to 1000 nm. They can contain one, two or up to 100 layers rolled on each other with an equidistant separation of 0.34 Å [2, 3, 4]. Later, Novoselov and Geim [5] made an enormous contribution to science with graphene discovery, whose laminar crystalline structure is composed entirely of carbon atoms with an sp2hybridization, with a thickness of only one atom of carbon. Graphene has unusual properties between a metal and a superconductor and high mechanical, elastic, and chemical resistance. Therefore, graphene has been studied and proposed for various applications in electronic, aerospace, automotive, medical, and food industries [6, 7, 8, 9, 10, 11, 12, 13].
Due to the ease of modifying its structure by incorporating other chemical elements, hybridization with functional groups, and decoration with organic molecules, carbon nanoparticle applications have been expanded enormously, leading to countless applications. For example, the miniaturization of electrical circuits composed of one or more carbon nanotubes, chemical and electromechanical sensors based on carbon nanotubes, the storage of hydrogen for fuel cells, the increase in charge capacity in batteries based on graphene or graphene nanoplatelets as well as the filtration capacity at the molecular level using graphene-based membranes, besides the reinforcement of polymeric matrices, to name only a few [4, 7, 11, 14, 15].
Materials science has been searching to generate new materials that possess a balance of properties, making them ideal for new and unexpected applications. Within this vast field are composite materials, which have a continuous phase (metallic, ceramic, or polymeric) and a discontinuous phase (filler or additive), which generally have high filler or additive contents of up to 70%, such as the case of titanium oxide (TiO2) or carbon black concentrates in a polyethylene matrix, since both additives are used as pigments in the plastics industry [16, 17]. With the beginning of nanotechnology and the growing supply of different carbon nanoparticles, a new class of materials has emerged called polymeric nanocomposites whose advantage lies in using a smaller quantity of particles to modify the behavior of the host matrix or continuous phase.
Electroconductive polymeric nanocomposites were originally based on graphite derivatives, later carbon nanofibers, carbon nanotubes (mono or multilayer), and recently on graphene or graphene nanoplatelets, as well as a wide variety of combinations between these and other nanoparticles with different nature and morphology [8, 17, 18, 19, 20]. In order to improve the electrical properties of these materials, combinations of carbon nanotubes have been made with graphite, graphene, clays, copper oxide, titanium oxide, silver nanowires, etc.; in all cases, the aim is to generate three-dimensional networks interconnected to facilitate the passage of electrons or phonons, to generate an electro/thermo-conductive material [21, 22].
In addition to providing the ability to conduct heat and electricity since they can exhibit the Peltier and Seebeck effect, [23, 24] such effects are beneficial in the development of thermoelectric materials, polymeric nanocomposites have also exhibited a noticeable improvement in mechanical properties, a barrier to gases, thermal stability [6, 9, 25, 26] as well as the ability to modify the electrical properties of the host matrix to generate materials for capacitors, electromagnetic and/or radiofrequency shields, have even allowed the development of metamaterials capable of modifying their refractive index, dielectric constant and/or Seebeck effect [27, 28, 29].
There are different methods for preparing polymeric nanocomposites, where the main objective up to now has been to achieve adequate dispersion and distribution of carbon nanoparticles that allow modulating the properties of the resulting material. Because carbon nanoparticles are held tightly together by van der Walls forces, different ways have been sought to separate them individually to combine them with a polymer later and obtain a homogeneous polymeric nanocomposite. The main methods employed to achieve this are briefly described below.
In this method, the polymer is dissolved in a suitable solvent with the aid of magnetic, mechanical and/or heat stirring to facilitate complete dissolution of the polymer. The carbon nanoparticles are suspended in the same liquid (solvent) or a combination of them, and magnetic, mechanical, or ultrasonic stirring is applied to improve the dispersion of the nanoparticles. Subsequently, both solutions are mixed and kept under stirring, then the solvents are evaporated with heat or slowly in an extraction hood (the above will depend on the nature and reactivity of the solvent). Finally, the resulting material, usually a dark-colored powder, is compacted by applying pressure and heat to obtain a useful material. At the laboratory level, it is the most used method for research purposes; however, the large amount of solvents used makes its scaling at an industrial level unfeasible [30, 31, 32].
In this method, one of the monomers or solvents used to obtain the polymer is mixed with the nanoparticles until a homogeneous dispersion is achieved; subsequently, the other reagents, including the corresponding catalysts, are added, and the polymerization reaction is carried out under the conditions of usual temperature and pressure. At the end of the reaction, the product obtained is purified, and the excess solvent is eliminated to recover the polymer formed with the incorporated nanoparticles. Given the complexity of this method, polyethylene’s polymerization in the presence of carbon nanotubes at the laboratory level and of polyamide 6 with nanoclays at an industrial level has been successfully reported [20, 33, 34].
This method is the most widely used at the laboratory level to obtain polymeric nanocomposites; it consists of passing the polymer and nanoparticles through a twin-screw extruder, whereby applying heat, the polymer melts and is transported by the screws that in turn impart shear forces to mix the components, in the different mixing zones that the extruder has. The mixture leaves the extruder, is cooled, and cut to obtain a polymeric nanocomposite. Due to its simplicity, this process can be easily scaled to an industrial level, in addition to the fact that it does not generate waste and does not use solvents [35].
Given the low affinity of polyolefins and in general of polymers for carbon nanoparticles, modifications have been made to the conventional melt mixing method by applying ultrasound waves in some specific sections of the extruder. It has been reported that this method can significantly improve the dispersion of nanoparticles of different nature and geometry, even with high nanoparticle content [36]. Different variants have evolved; the main difference being the mode of generation and application of ultrasound waves; conventionally fixed frequency ultrasound waves are generated, which are applied constantly or intermittently [37]. In another embodiment, the ultrasound waves are applied constantly, gaining a dynamic frequency sweep in a given interval [35, 38, 39].
There are other methods used for the production of polymeric nanocomposites, mainly at the laboratory level. Nevertheless, the choice of method will broadly define the level of dispersion and distribution of the nanoparticles within the polymeric matrix, and therefore the properties of the resulting material.
In Table 1, the most outstanding reports in electro/thermo-conductive polymer nanocomposites of the last five years are presented to have a broader outlook on the subject. By their nature, polyolefins are good electrical insulators exhibiting electrical conductivity in the order of 10−12 to 10−15 S/cm. As can be seen, different techniques have been used for the preparation of polymeric nanocomposites, achieving fascinating results. It can also be seen that the most popular preparation method is melt mixing, which, as mentioned above, is a versatile and easily scalable method. Another variant that can be observed is that depending on the polymeric matrix; the result will change; even more important is the concentration of nanoparticles used. Another aspect that should be highlighted is the modification or doping of the carbon nanoparticles, which slightly increases this property. Finally, as is known, polyolefins are thermal insulators, and their thermal conductivity ranges between 0.1 to 0.4 W/mK. Thermal conductivity has also shown sharp increases, as shown in Aghelinejad and Leung’s reports and Paszkiewicz et al. [45, 50], where the matrix used was polyethylene.
System | σ (S/cm) | Weight (%) | κ (W/mK) | Method of preparation | Ref |
---|---|---|---|---|---|
PS/SSWCNTa | 1.25x105 | 75 | 0.30 | Ball milling | [40] |
PVC/CNT | 2.3x10−1 | 61 | 0.06 | Drop casting | [41] |
PP/MWCNTb,c PP/MWCNTd PP/MWCNTe PP/MWCNTf | 1x10−10 1x10−7 1x10−4 1x10−3 | 8 | — | Melt mixing | [38] |
PS-LDPE/MWCNT | 2.9x10−3 | 1.5 | — | Melt mixing | [42] |
PVC/CNT | 2.4x10−2 | 25 | — | Solution | [24] |
HDPE/CNTg HDPE/CNTh | 2x10−4 5.8x10−5 | 15 | 0.60 0.06 | Melt mixing | [43] |
PP/MWCNTi,c PP/MWCNTd PP/MWCNTe PP/MWCNTf | 1x10−5 1x10−4 1x10−3 1x10−2 | 8 | — | Melt mixing | [39] |
PVC/SG-CNTj | 3.35x102 | 66 | 0.18 | Drop casting | [24] |
LDPE/MWCNT | 2.38x10−2 | 5 | — | Solution | [44] |
LDPE/MWCNT LDPE/GNP | 2x10−2 1x10−6 | 20 | 0.67 0.58 | Melt mixing | [45] |
PP/CNTk PP/CNTl PP/CNTm PP/CNTn PP/CNTo | 1.6x10−2 9.56x10−1 1.21x10−1 1x10−3 1.05x10−1 | 2 | — | Melt mixing | [46] |
mLLDPE/MWCNT | 2.8x10−4 | 10 | — | Melt mixing | [47] |
LDPE/G LDPE/SWCNT | 1.0x10−5 8.3x10−5 | 3 | — | Melt mixing | [48] |
PP/SWCNT PP/B-SWCNTp | 1.21x10−1 3.58x10−1 | 2 | 0.28 | Melt mixing | [49] |
PP/N-MWCNTn | 4 x10−2 | 5 | 0.28 | Melt mixing | [28] |
Electric/thermal parameters of the most relevant polymer nanocomposites with carbon nanoparticles.
SSWCNT small-bundle-diameter-single-walled CNTs.
PP MFI = 34 g/10 min.
Melt extruded without ultrasound.
Melt extruded with ultrasound fixed frequency.
Melt extruded with ultrasound variable frequency.
Melt extruded previously dispersed in gas phase.
Solid.
Foam.
PP MFI = 1200 g/10 min.
SG-CNT supergrowth-CNT.
CNT, NC700.
CNT, CNS-PEG.
CNT, Tuball.
CNT, N-MWCNT A1, Nitrogen doped.
CNT, N-MWCNT IFW, Nitrogen doped.
Boron doped SWCNT.
The motivation of present work was to perform a screening of several carbon nanoparticles to obtain polymeric nanocomposites with a better balance on properties such as electro/thermal conduction, mechanical and thermal stability. For this purpose, different carbon nanoparticles were selected. Their main differences lie in morphology (laminar versus fibrillar), structure (flat versus rolled layers), and functionalization (modified versus un-modified surface, i.e., CNT). Besides, the use of different polyolefins such as polyethylene and polypropylene, which bear significant differences in structure. On the one hand, polyethylene possesses a main chain almost free of pendant groups; meanwhile, polypropylene’s main chain contains one methylene group each three carbon atoms. The best candidate is expected to be used to manufacture prototypes of thermistors (temperature sensors based on a change in electrical resistivity).
In the following section, the preparation of polymeric nanocomposites in high-density polyethylene (PE) and polypropylene (PP) and their combination with four types of carbon nanoparticles (CNP) are presented and discussed. In all cases, a content of 20% wt/wt of each nanoparticle was used. The characterization results by thermogravimetric analysis, mechanical properties in tension and bending, electrical resistivity, and dielectric constant as a function of frequency and thermal conductivity are also presented. The resins used to obtain the polymeric nanocomposites were the following: high-density polyethylene (PE) Alathon H4620 with MFI of 20 g/10 min and density of 0.940 g/cm3 provided by LyondellBasell (TX, USA), also polypropylene (PP) Formolene 4111 T with MFI of 35 g/10 min and density of 0.9 g/cm3 provided by Formosa Plastics, (Tamaulipas, Mexico). The carbon nanoparticles used and their main characteristics are listed in Table 2.
Material | Density (g/cm3) | SSA* (m2/g) | Average length (μ) | Average diameter (nm) | Purity (%) | Supplier |
---|---|---|---|---|---|---|
CNT1 | 2.1 | 200 | 20 | 20 | 90 | CheapTubes, Inc |
MCNT2 | 2.1 | 110 | 20 | 20 | 90 | CheapTubes, Inc |
GNP3 | 2.1 | 600 | 2 | — | 97 | CheapTubes, Inc |
CB4 | 2.1 | 240 | — | 15 | 95 | Cabot Corp. |
Characteristics and properties of the different carbon nanoparticles.
SSA, Specific surface area.
CNT industrial grade.
MCNT, Industrial grade modified CNT with -COOH contain 1.2% of COOH groups.
GNP, industrial grade graphene nanoplatelets.
Carbon Black, Vulcan XC72 grade.
The materials’ processing was carried out in a Thermo Scientific model PRISM 24MC twin-screw extruder; the diameter of the screws is 24 mm with a length/diameter ratio of 40:1. According to the formulation, a controlled feeder for powders and another for the resin were used, which were previously calibrated to dose the required amount. The addition of the nanoparticles and the resin was carried out simultaneously in the extruder. A screw rotational speed of 100 rpm was used, a flat temperature profile of 180 and 200°C for the nanocomposites with PE and PP, respectively. Under these conditions, a production speed of 3.2–3.5 Kg/h was obtained. To improve the nanoparticle’s agglomerates’ dispersion and distribution, a device specially designed to irradiate the extruded material with ultrasound waves was coupled at the extruder exit. The device consists of a chamber with controlled temperature; inside, there is a 12.5 mm diameter titanium catenoid sonotrode (Branson Corp.) connected to a homemade ultrasound wave generator, which can generate ultrasonic waves in the range of 10 to 50 kHz, with a 750 W power [35, 38]. Finally, the material was passed through a water bath and cutter. Subsequently, each material was compression-molded to obtain a 15 X 15 X 0.2 cm plate, and a PHI press was used, a pressure of 20 Tn, with temperatures of 180 and 200°C for the nanocomposites with PE and PP, respectively. Specimens were cut for the characterization of the polymeric nanocomposites.
The characterization of the polymeric nanocomposites was carried out using the following analytical techniques. The thermogravimetric analysis (TGA) was carried out using a thermogravimetric analyzer from TA Instruments model Q500, using a sample of approximately 8 mg, a temperature range of 25–600°C, with a heating rate of 10°C/min and an inert atmosphere with nitrogen gas with a flow of 50 ml/min. The mechanical properties were evaluated in a universal testing machine, Instron model 1000, for tension tests in accordance with the ASTM D638 standard, using V-type specimens and a stretched speed of 50 mm/min and a load cell of 10 kN. The flexion tests were carried out according to the ASTM D790 standard using 12 X 1.25 X 0.2 cm specimens in 3-point bending mode; in both cases, five measurements were made, and the average value was reported. The electrical properties of resistance and capacitance were measured with an LCR analyzer in samples of 1 X 1 X 0.2 cm, both faces of the specimen were covered with silver paint, and a copper wire was placed as an electrode. The measurement was carried out at room temperature using a frequency range from 20 Hz to 2 kHz in increments of one decade; 5 measurements were made, and the average value was reported. The thermal diffusivity determination was carried out in a TA Instruments thermal diffusivity analyzer Discovery Xenon Laser Flash model (DXF-200). The analyzed specimen had circular geometry with 12.5 x 2 mm dimensions; both faces were coated with carbon paint and one of them with silver paint to ensure good contact with the temperature sensors; the measurement was carried out in triplicate at 25°C.
The study of the thermal stability in electrically conductive materials is of great importance because when an electric current circulates through them, they can undergo heating and alter their behavior or ability to conduct electricity. On the other hand, this analysis makes it possible to determine the thermal stability of the materials and the amount of mass that they can lose due to the effect of temperature in a controlled atmosphere. It should be mentioned that if the atmosphere is air, thermo-oxidative degradation will occur. In Figure 1, the corresponding thermograms to the nanocomposites based on PE and PP are presented. While in Table 3, the specific data for the mass loss of T5% and T50% are shown.
Thermal stability by TGA of polymeric nanocomposites with 20% wt/wt of different CNP, (A) PE base, and (B) PP base.
Material | Polyethylene | Polypropylene | ||
---|---|---|---|---|
T5% | T50% | T5% | T50% | |
Polymer | 337.50 | 415.67 | 373.49 | 437.59 |
CNT | 411.28 | 447.81 | 420.09 | 451.99 |
MCNT | 417.68 | 452.17 | 423.69 | 453.15 |
GNP | 416.88 | 446.27 | 402.26 | 445.07 |
CB | 430.27 | 451.89 | 419.47 | 449.98 |
Degradation temperatures at T5%, T50%, of polymeric nanocomposites with different carbon nanoparticles.
It can be observed that PE exhibits a loss of mass from 330°C, while polymeric nanocomposites exhibit this loss at a temperature around 411°C, regardless of the type of nanoparticle used. It is important to note that the nanocomposite containing CB exhibits the highest thermal stability. For PP, degradation begins at a temperature of 370°C, while for polymeric nanocomposites occurs around 420°C, regardless of the type of nanoparticle used. In this case, nanocomposites based on CNT and MCNT exhibit the highest thermal stability of all.
Various reports in the literature suggest that carbon nanoparticles provide greater thermal stability or heat resistance to polymers in general due to a mechanism based on the formation of a carbonaceous layer and a tortuous path similar to a labyrinth on the surface of the material that prevents the release of combustion gases [19, 26]. This analysis is of great importance for flame retardancy applications in aeronautics, automotive, and textile industries and to determine the safety temperature that the material can support before molten and inflamed by the passage of an electrical current.
The mechanical properties of polymeric nanocomposites are of great interest because, as mentioned above, the addition of carbon nanoparticles can improve their performance. In Table 4, the properties of the PE and PP-based nanocomposites with the different carbon nanoparticles are listed.
Material | Polyethylene | Polypropylene | ||||
---|---|---|---|---|---|---|
Tensile modulus (MPa) | Elongation (%) | Flexural modulus (MPa) | Tensile modulus (MPa) | Elongation (%) | Flexural modulus (MPa) | |
Polymer | 23.68 | 747 | 376 | 33.28 | 571 | 289 |
CNT | 41.99 | 1 | 965 | 43.05 | 1 | 862 |
MCNT | 38.84 | 1 | 989 | 38.7 | 1 | 800 |
GNP | 42.03 | 1 | 1052 | 42.13 | 1 | 980 |
CB | 40.47 | 1 | 951 | 44.22 | 1 | 913 |
Mechanical properties of polymeric nanocomposites with different carbon nanoparticles.
As expected, with the addition of nanoparticles, the different properties were modified; firstly, the PE exhibits a tensile modulus of 23.68 MPa, while the nanocomposites present a maximum increase of 180%, this increase in resistance to stress causes the elongation of the material to be markedly reduced, suggesting that the stiffness of the material has changed from a ductile to a brittle material, in which plastic deformation has been suppressed. For its part, the flexural modulus corroborates the above since PE has a value of 376 MPa, and in nanocomposites, this value has increased to 280%. A similar behavior occurs with PP, exhibiting an increase of 130% and 330% in the tensile and flexural modulus, respectively. In this sense, the greatest increase in mechanical properties for polyethylene is obtained with GNP > CNT > CB > MCNT, while for polypropylene, it is CB > CNT > GNP > MCNT. In this sense, it is worth mentioning that the surface modification made to the MCNTs did not improve by itself, the compatibility with the host matrix PE or PP.
In the literature, many reports can be found that mention the improvement in mechanical properties in polymeric nanocomposites reinforced with carbon nanoparticles. However, the addition of compatibilizing agents such as maleic anhydride grafted to the resin is required to achieve a substantial increase in the mechanical properties, even with low amounts of carbon nanoparticles [9, 26, 51, 52]. Due to the lightweight and high modulus obtained by the polymeric nanocomposites reinforced with carbon nanoparticles, aeronautics and automotive industries would be benefited from the development of these materials for different components, which can provide a reduction in weight and lower consumption of fuels.
The evaluation of electrical properties was carried out using an LCR as a function of a frequency interval, as shown in Figure 2. First, the polyethylene-based system allows observing that the PE resin exhibits the highest electrical resistance values at low-frequency values; above 10 kHz, the material becomes polarized and shows a lower electrical resistance, which decreases three orders of magnitude when reaching 2 MHz. With the addition of GNP, the material exhibits a behavior similar to that of PE, one order of magnitude lower in terms of electrical resistance. Meanwhile, the materials that contain MCNT and CNT show a reduction of 7 and 8 orders of magnitude; however, the polarization effect occurs when reaching high frequencies of 100 kHz. The CB-based system exhibits the least electrical resistance with nine orders of magnitude reduction concerning PE alone. In addition to not showing polarization effects as a function of frequency, which suggests that it behaves as an excellent electrical conductor.
Electrical resistance as a function of frequency, of polymeric nanocomposites with 20% wt/wt of different CNP, (A) PE base, and (B) PP base.
For materials based on PP, the behavior is slightly different PP only presents the highest values of electrical resistance at low-frequency values; above 10 kHz, the material is polarized and shows a lower electrical resistance, which decreases three orders of magnitude when reaching 2 MHz, in the same way as the PE. Surprisingly, the CB-based system exhibits an electrical resistance that is completely dependent on the frequency. When it increases, the electrical resistance decreases to four orders of magnitude concerning the PP, suggesting that the material behaves like a semiconductor. On the other hand, the materials that contain CNT and MCNT show a reduction of seven and eight orders of magnitude without presenting the polarization effect in the entire frequency range, which suggests that they behave like a good electrical conductor. Finally, the compound containing GNP shows the lowest electrical resistance with a reduction of nine orders of magnitude and a linear response throughout the entire frequency range used. Based on the above, it can be pointed out that the nature of the polymeric matrix and the type of carbon nanoparticle can notably modify the electrical behavior of the polymeric nanocomposite [8, 31, 53, 54].
The behavior of the dielectric constant of polymeric nanocomposites is presented in Figure 3. Analogously to the behavior of electrical resistance, the dielectric constant follows a similar trend with the addition of carbon nanoparticles. The PE has a value of 3 and a linear behavior in the entire frequency range, while the nanocomposite with GNP shows an increase of 1 order of magnitude and a linear behavior as a function of frequency. Materials containing CNT and MCNT show an increase of three orders of magnitude for PE, with a slight decrease at high frequencies. The material that contains CB exhibits a frequency-dependent behavior since, at 20 Hz, it shows an increase of four orders of magnitude and then it decreases two orders of magnitude from a frequency of 1 kHz; this behavior corresponds to that of a capacitor, capable of storing energy and releasing it suddenly when used in electrical/electronic circuits.
Dielectric constant of polymeric nanocomposites with 20% wt/wt of different CNP, (A) PE base, and (B) PP base.
On the other hand, PP exhibits a dielectric constant of 3 and does not vary as a function of frequency; the nanocomposite with CB shows an increase of one order of magnitude with respect to pure PP, while the nanocomposites with CNT and MCNT show an increase in 3 orders of magnitude and a slight decrease at high-frequency values. Finally, the nanocomposite with GNP presents the highest value of dielectric constant, with an increase of up to four orders of magnitude at a frequency of 20 Hz, and decreases by one order of magnitude for the rest of the frequencies evaluated. Similar to the behavior of PE nanocomposites, PP-based nanocomposites exhibit capacitor-like behavior throughout the evaluated frequency range.
The combination of properties for these new nanocomposite materials results in various applications that had not been previously conceived. For example, supercapacitors can be manufactured for systems that require a precise regulation of the supplied energy and a high energy storage capacity, and that in this way, the energy necessary to drive an electrical component can be supplied without the need to overload the electrical network of the circuit, besides not present a memory effect [25, 31]. Another field of interest for those materials would be the packaging industry, with the development of antistatic, static dissipative or semiconductive packages, for the protection of electronic components during their transportation, even for EMI or RF shielding for aerospace and defense to protect safety- and mission-critical systems from intentional and unintended electronics emissions [44]. The growing industry of electronic textile or smart textiles that develop wearable technology requires integrating textile fibers capable of conducting electrical signals. There are fabrics in which electrical and electronic elements such as microcontrollers, sensors, and actuators have been integrated that allow clothing to react, send information, or interact with the environment [55, 56, 57].
The study of the thermal properties of polymeric nanocomposites intended for electronics applications is of great importance since, as mentioned above, the passage of electric current can induce a temperature gradient in electrical conductors, even in metals. The heat capacity was first determined, as well as the density and thermal diffusivity to determine the thermal conductivity of polymer nanocomposites. Values are shown in Table 5.
Polyethylene | Polypropylene | |||
---|---|---|---|---|
Cp (J/gK) | κ (W/mK) | Cp (J/gK) | κ (W/mK) | |
Polymer | 1.846 | 0.24 | 1.917 | 0.28 |
CNT | 1.671 | 0.43 | 1.672 | 0.32 |
MCNT | 1.643 | 0.25 | 1.639 | 0.34 |
GNP | 1.736 | 0.31 | 1.477 | 0.25 |
CB | 1.495 | 0.28 | 1.569 | 0.30 |
Heat capacity (Cp, J/g K) and thermal conductivity (κ, W/m K) of polymeric nanocomposites with different carbon nanoparticles.
According to the data reported in Table 5, PE has the highest value of Cp; with the addition of the different nanoparticles, the Cp of the nanocomposites decreases significantly, the most notable case being the nanocomposite with CB. Meanwhile, PP exhibits an even higher Cp than PE, while the addition of the different nanoparticles promotes a decrease in this value, with graphene nanoplatelets being the material that most reduces this value. The decrease in Cp of the different nanocomposites can be associated with the ease they present for heat conduction, making the material less thermally insulating.
On the other hand, the thermal conductivity presents substantial improvements; in general, the PE-based nanocomposites exhibit the most significant increase in thermal conductivity 79, 29, 16, and 4% for the nanoparticles in the following order CNT > GNP > CB > MCNT, suggesting that carbon nanotubes are the most effective additive to increase the thermal conductivity of the nanocomposite. The trend is reversed, with increases of 21, 14, 7, and − 11% for MCNT > CNT > CB > GNP for PP-based nanocomposites. Although the Cp of the nanocomposites follows a different trend towards thermal conductivity, it should be mentioned that the type of polymeric matrix, the morphology, distribution, and dispersion of the different nanoparticles play an important role in heat conduction. This phenomenon is carried out through phonons; therefore, if there are spaces in the material in which the nanoparticles are too far apart, the phonons’ passage through the material will find a physical barrier for their passage.
Recent reports suggest that a polymeric nanocomposite’s thermal conductivity can be affected by different factors, including the processing method, the number of defects in the carbon nanoparticles, and, finally, their dispersion within the polymeric matrix [21, 29, 45, 46, 58]. The capability to conduct heat in a polymeric nanocomposite makes an ideal candidate for different applications such as heat exchangers, solar water heaters, thermoelectric materials, electrical heaters, to mention a few [22]. These devices will take advance of the lightweight, mechanical strength, thermal and dimensional stability of these materials, in which automotive, construction, and green industries are interested.
The electrical resistivity of polymeric nanocomposites with carbon nanoparticles shows an anomalous increase near the melting point of the matrix; this effect is known as a positive temperature coefficient (PTC) of resistivity. On the other hand, the negative temperature coefficient (NTC) is a very sharp decrease in resistivity when the temperature is above the melting point of semicrystalline polymers. These kinds of materials have important industrial applications like overcurrent protectors and self-regulating heaters [59, 60].
The polymer nanocomposites obtained were evaluated for their potential use as a thermistor. For this purpose, a prototype will be constructed; it consists of a square piece with dimensions 1 X 1 X 0.2 cm; both sides were cover with silver paste as an electrode and a copper wire. Kapton tape was used to cover the prototype and isolate the wires during the heating cycle. A Mettler Toledo FP82 Hot Stage was used to supply heat in an interval from 40 to 160°C at a heating rate of 5°C/min, the Hot Stage was connected to a Mettler Toledo FP90 Central Processor, the electrical resistivity was measured with a Keithley Source Meter model 2400, in a 4-wire sense mode, to avoid the parasite signal in the circuit.
As seen in Figure 4, all the polymer nanocomposites exhibit thermistor behavior, i.e., an increase of resistivity around 128°C. The intensity of the PTC (the electrical resistivity ratio at the melting point versus room temperature) depends on the type of carbon nanoparticle used. The interval of temperature at which this phenomenon occurs is between 127 and 131°C. In this sense, the intensity of the PTC is in the following order GNP > CNT > MCNT > CB. This behavior could be associated with the capability of the polymer chains to break apart the conductive pathway formed in the polymer nanocomposite, due to the semicrystalline nature of the polymer matrix and the reduction in viscosity, during the heating. It is worth mentioning that PE/CB nanocomposite exhibits the lowest PTC intensity, probably due to the high structure of the CB (CB possess the small average particle size) and could form new conductive pathways in the molten state as stated by Zeng et al. [61].
Temperature versus electrical resistivity of PE base polymeric nanocomposites with 20% wt/wt of different CNP.
The polymer nanocomposites with carbon nanoparticles become an electrically conductive material whit the addition of a certain amount of carbon nanoparticles; this property is fundamental in electrical and electronic applications. For many years, carbon black has been chosen as the best candidate for this purpose; with other carbon nanoparticles such as CNF, CNT, GO, graphene, and their combination with other materials, significant improvements have been made for electrically conductive materials.
In this work, the preparation and characterization of electrically conductive polymeric nanocomposites with different carbon nanoparticles was addressed to screen the type of carbon nanoparticles that allows them to obtain polymeric nanocomposites with a better balance on properties such as electro/thermal conduction, mechanical, and thermal stability. A material with the desired properties for their application in electronics, such as low electrical resistivity, thermal stability, and mechanical strength, besides thermal conductivity, is PE/CB polymeric nanocomposite since it exhibits a better balance of properties. This set of properties makes them candidates for use in various applications. Besides thermistors, they may be candidates for use in electrical heaters, which are a kind of electrical resistor used to converts electrical energy into thermal energy, as thermoelectric materials for their use in the exploitation of renewable energies, in heat exchangers, as EMI and RFI shielding, and as a wearable textile for smart applications.
The authors are grateful for the support of the CIQA technical staff for the preparation and characterization of materials: María G. Méndez Padilla, Gilberto F. Hurtado López, Rodrigo Cedillo García, Juan F. Zendejo Rodríguez and Jesús G. Rodríguez Velazquez. The financial support by SENER-CONACyT-CeMIE-SOL through the 207450-12 project is also appreciated.
The authors declare no ‘conflict of interest’.
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