Thermophysical properties of some common PCMs with high latent heat.
\\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:null},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:"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:"4549",leadTitle:null,fullTitle:"A Concise Review of Molecular Pathology of Breast Cancer",title:"A Concise Review of Molecular Pathology of Breast Cancer",subtitle:null,reviewType:"peer-reviewed",abstract:"Cancer is one of the leading causes of death in most countries and its consequences result in huge economic, social and psychological burden. 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It is hoped that this book will contribute to development of novel diagnostic as well as therapeutic approaches, which lead to cure of breast cancer.",isbn:null,printIsbn:"978-953-51-2030-8",pdfIsbn:"978-953-51-7234-5",doi:"10.5772/58669",price:119,priceEur:129,priceUsd:155,slug:"a-concise-review-of-molecular-pathology-of-breast-cancer",numberOfPages:234,isOpenForSubmission:!1,isInWos:1,hash:"defcba71c9acb69a0f9c99264c4856c5",bookSignature:"Mehmet Gunduz",publishedDate:"March 25th 2015",coverURL:"https://cdn.intechopen.com/books/images_new/4549.jpg",numberOfDownloads:12747,numberOfWosCitations:12,numberOfCrossrefCitations:6,numberOfDimensionsCitations:14,hasAltmetrics:0,numberOfTotalCitations:32,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"May 29th 2014",dateEndSecondStepPublish:"June 26th 2014",dateEndThirdStepPublish:"September 23rd 2014",dateEndFourthStepPublish:"December 22nd 2014",dateEndFifthStepPublish:"January 21st 2015",currentStepOfPublishingProcess:5,indexedIn:"1,2,3,4,5,6",editedByType:"Edited by",kuFlag:!1,editors:[{id:"38384",title:"Prof.",name:"Mehmet",middleName:null,surname:"Gunduz",slug:"mehmet-gunduz",fullName:"Mehmet Gunduz",profilePictureURL:"https://mts.intechopen.com/storage/users/38384/images/4236_n.jpg",biography:"Dr. Gunduz graduated from the Faculty of Medicine of Hacettepe University in Ankara, Turkey in 1990. He did residency at the department of otolaryngology in the same university from 1990 to 1994. From 1995 to 2009, he studied and worked in Japan in the field of his majors of otolaryngology head and neck surgery as well as human genetics in Wakayama Medical University and Okayama University Graduate School of Medicine, Dentistry and Pharmaceutical Sciences at various academic levels (from PhD student in human genetics to assistant professor). He has passed Japanese Medical Board. During this period, he led a discovery and identification of roles of several cancer-related genes such as ING1 and ING3. He has also been a visiting scientist in MD Anderson Cancer Center, University of Texas, Houston, USA. From 2009 to 2011, he worked as associate professor in Fatih University Medical School. From 2011 to 2013, he served as professor in Fatih University. From February 2013 to currently, he is now professor and Dean of Medical School in Turgut Ozal University. He both serves as surgeon of otolaryngology including cochlear implant and other neurootological operations as well as coordinator for researchers in the department of medical genetics in various projects including cancer, deafness, obesity and neurodegenerative diseases. 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\r\n\tThis book will focus on the wide specter of mucosal inflammation intending to provide the reader with a comprehensive overview of the current knowledge on the topic. More and more studies are focused on finding different aspects of mucosal inflammation since it is involved in the pathogenesis of many diseases - from gut to lungs, urogenital system, etc. To better understand the causes of its occurrence as well as the search for therapeutic strategies, many resources are invested in scientific developments in this field.
\r\n\r\n\tFacts about the role of calprotectin and other biomarkers were accumulated. Participation of neutrophils appears an attractive way to explain the involvement of different subpopulations of immunocompetent cells and cytokines in mucosal inflammation. Over the last five years, scientific developments in the field have discovered more genes involved in the pathogenesis of mucosal inflammation elucidating the interaction of innate immune mechanisms with the microorganisms in the gut and their role in maintaining intestinal homeostasis. Besides, the science aims at identifying and characterizing immune and non-immune cells involved in the emergence and maintenance of chronic inflammation.
\r\n\r\n\tThe book aims to cover the developing diagnostic methods for identifying the mucosal inflammation, towards a better analysis of the inflammation, understanding of the relationship between genetic and proteomic markers and response to therapy; and improving therapeutic options for patients who have mucosal inflammation.
",isbn:null,printIsbn:"979-953-307-X-X",pdfIsbn:null,doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"2e7bde3621cdf64518356b76e3132542",bookSignature:"Dr. Tsvetelina Velikova",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/8843.jpg",keywords:"Inflammation, Neutrophils, Cytokines, Mucosal Biomarkers, Gut Tolerance, Antigen Tolerance, Mayo Score, Lesions, Acute Inflammation, Chronic Inflammation, Gut Permeability, Asthma",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"June 16th 2020",dateEndSecondStepPublish:"July 7th 2020",dateEndThirdStepPublish:"September 5th 2020",dateEndFourthStepPublish:"November 24th 2020",dateEndFifthStepPublish:"January 23rd 2021",remainingDaysToSecondStep:"8 months",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:"Dr. Velikova research focuses on autoimmune disorders, such as celiac disease, IBD, diabetes, asthma, as well as on the delicate autoimmunity mechanisms involving Th17 and Treg cells, cytokines, biomarkers, novel biologic therapies. She has been engaged in fifteen projects in the field of immunology and internal medicine. She is an editorial board member and reviewer for several medical journals and has publications in eminent journals and book chapters in the field of gastrointestinal immunology.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"180979",title:"Dr.",name:"Tsvetelina",middleName:null,surname:"Velikova",slug:"tsvetelina-velikova",fullName:"Tsvetelina Velikova",profilePictureURL:"https://mts.intechopen.com/storage/users/180979/images/system/180979.jpg",biography:"Dr. Tsvetelina Velikova received her MD and Ph.D. degrees, both with honors, from the Medical University of Sofia, Bulgaria. Subsequently, she became involved in active immunology research and teaching. Dr. Velikova also received advanced training in Clinical Immunology at University Hospital St. Ivan Rilski, Sofia, Bulgaria. \r\nShe is currently an assistant professor of Clinical immunology affiliated to the Sofia University and University Hospital Lozenetz, Bulgaria. \r\nHer research focuses on autoimmune disorders, such as celiac disease, IBD, diabetes, asthma, as well as on the delicate autoimmunity mechanisms involving Th17 and Treg cells, cytokines, biomarkers, novel biologic therapies and their implication in clinical practice.\r\nDr. Velikova has been engaged in fifteen projects in the field of immunology and internal medicine. She is an editorial board member and reviewer for several medical journals and has publications in eminent journals and book chapters in the field of gastrointestinal immunology.",institutionString:"Lozenetz Hospital",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"Lozenetz Hospital",institutionURL:null,country:{name:"Bulgaria"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"16",title:"Medicine",slug:"medicine"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"177731",firstName:"Dajana",lastName:"Pemac",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/177731/images/4726_n.jpg",email:"dajana@intechopen.com",biography:"As a Commissioning Editor at IntechOpen, I work closely with our collaborators in the selection of book topics for the yearly publishing plan and in preparing new book catalogues for each season. This requires extensive analysis of developing trends in scientific research in order to offer our readers relevant content. Creating the book catalogue is also based on keeping track of the most read, downloaded and highly cited chapters and books and relaunching similar topics. I am also responsible for consulting with our Scientific Advisors on which book topics to add to our catalogue and sending possible book proposal topics to them for evaluation. Once the catalogue is complete, I contact leading researchers in their respective fields and ask them to become possible Academic Editors for each book project. Once an editor is appointed, I prepare all necessary information required for them to begin their work, as well as guide them through the editorship process. I also assist editors in inviting suitable authors to contribute to a specific book project and each year, I identify and invite exceptional editors to join IntechOpen as Scientific Advisors. I am responsible for developing and maintaining strong relationships with all collaborators to ensure an effective and efficient publishing process and support other departments in developing and maintaining such relationships."}},relatedBooks:[{type:"book",id:"6550",title:"Cohort Studies in Health Sciences",subtitle:null,isOpenForSubmission:!1,hash:"01df5aba4fff1a84b37a2fdafa809660",slug:"cohort-studies-in-health-sciences",bookSignature:"R. Mauricio Barría",coverURL:"https://cdn.intechopen.com/books/images_new/6550.jpg",editedByType:"Edited by",editors:[{id:"88861",title:"Dr.",name:"R. Mauricio",surname:"Barría",slug:"r.-mauricio-barria",fullName:"R. 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"878",title:"Phytochemicals",subtitle:"A Global Perspective of Their Role in Nutrition and Health",isOpenForSubmission:!1,hash:"ec77671f63975ef2d16192897deb6835",slug:"phytochemicals-a-global-perspective-of-their-role-in-nutrition-and-health",bookSignature:"Venketeshwer Rao",coverURL:"https://cdn.intechopen.com/books/images_new/878.jpg",editedByType:"Edited by",editors:[{id:"82663",title:"Dr.",name:"Venketeshwer",surname:"Rao",slug:"venketeshwer-rao",fullName:"Venketeshwer Rao"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"4816",title:"Face Recognition",subtitle:null,isOpenForSubmission:!1,hash:"146063b5359146b7718ea86bad47c8eb",slug:"face_recognition",bookSignature:"Kresimir Delac and Mislav Grgic",coverURL:"https://cdn.intechopen.com/books/images_new/4816.jpg",editedByType:"Edited by",editors:[{id:"528",title:"Dr.",name:"Kresimir",surname:"Delac",slug:"kresimir-delac",fullName:"Kresimir Delac"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"53283",title:"Lesser Known Aromatic Plants in Nigeria",doi:"10.5772/66484",slug:"lesser-known-aromatic-plants-in-nigeria",body:'\nAromatic herbs and spices are widely used in Nigeria for culinary and medicinal purposes. While some are quite common and used worldwide, others like: wild ginger (Siphonochilus aethiopicus (Schweinf) B.L Burtt), African nutmeg (Monodora myristica (Gaertn) Dunal) and sacred garlic pear (Crateva adansonii DC) are not. Herbs and spices make important contributions towards the odour and flavour of foods due to the presence of volatile (essential) oils and fixed oils. They confer new aromas to the foods, and their use for improving the taste of foods is a cultural achievement of all races which also led to cultural exchanges very early in history [1]. Moreover, there is an increasing interest in using the extracts of herbs and spices, for food preservation [2] since as natural foodstuffs, they appeal to many consumers who question the safety of synthetic food additives due to their carcinogenicity or other concerns [3, 4]. Indeed, since prehistoric times, herbs were the basis for nearly all medicinal therapy until synthetic drugs were developed, and even today, herbs are still found in 40% of prescription drugs [5].
\nThus, in addition to imparting characteristic pleasant flavours, certain herbs and spices prolong the storage life of foods by preventing rancidity through their anti-oxidant activity or through bacteriostatic or bactericidal activity [6]. Consequently, herbs and spices have medicinal values, anti-oxidant and anti-microbial properties [7], and some do contain potent phytochemicals, which provide significant protection against cancer [8].
\nWild ginger is an herb with perennial tuberous roots giving rise to annual leafy stems which grows in sub-Saharan Africa especially in savannah regions or regions with dry season [9]. It belongs to the family Zingiberaceae and has leafy shoots (pseudo-stem) which grow to about 35 cm high after flowering and is common throughout the West African region and elsewhere in tropical Africa [9]. The rhizomes which have a terrific scent of violets and ginger are spindle shaped and are about 5 cm by 1 cm, arranged radially on lateral roots that spread fairly readily underground [9]. The Nigerian variety flowers between April and May after the early rains and the flowers, which appear before the leaves, come up in considerable quantity followed by the leaves and the pseudo-stem [10]. The flowers, just borne above ground level in inflorescences separate from the leafy shoot, are purple with white corolla tube and a yellow flare on the central petal and are 7–10 cm long [9]. The leafy shoot dries up between September and December after which it falls off. The herb is found in the wild and could also be cultivated.
\nThe South African variety is a deciduous aromatic plant, bisexual or female, up to 1 m high and sprout annually from the underground stem in spring [11]. The leaves are glabrous and 30–400 × 50–90 mm in size, light green, lance shaped and borne on the end of stem-like leaf bases [11, 12]. Between October and February, it gives faintly scented flowers that are white to bright pink with yellow markings on lip, white corolla tubes 30–40 mm long and tepal lobes 60–80 mm wide [12]. The tremendously attractive flowers often appear before the leaves in spring, perhaps to allow them to be more visible to pollinators [13]. They may also vary in colour from bright pink, purple-pink, yellow to white with a yellow centre and are delicately scented. About 15 flowers are produced per plant over the flowering season, each lasting a single day [14].
\nThe roots, tubers and rhizomes of wild ginger are used for their aroma and medicinal properties in the West and South of Africa. While they are used as spice by the Igede people of Benue State of Nigeria [15], others mainly use them in traditional medicine for colds, coughs, influenza, hysteria, pain and malaria amongst other ailments [16, 17]. It is also used by Zulu people as a protection against lightning and snakes [18]. Infusions of the rhizome and roots are anti-inflammatory (prostaglandin synthetase inhibition), bronchodilatory, smooth muscle relaxant, mild sedative, anti-candidal and used to treat headache, influenza, mild asthma, sinusitis, sore throat, thrush, epilepsy, hysteria and relieve dysmenorrhoea [11] or administered to horses as prophylactics against horse sickness [19]. It is in such popular demand and coupled with the method of harvesting which involves removal of the entire rhizome that it has become extinct in certain areas [20]. The plant does not set much seed and splitting rhizomes is the best available option for plant propagation [14].
\nThe seeds of Monodora myristica (Gaertn.) Dunal either fresh or roasted are used both as a spice in cuisine and medicinally in different parts of Africa and in the Caribbean [21, 22]. It is largely underutilized and has recently been used as popcorn flavouring in an attempt to increase its utilization [23]. It is also responsible for the distinct flavour of the Nigerian delicacy “isi ewu”, and it is used in soups and peanut paste [23, 24]. Its aroma which is enhanced by mild roasting is similar to nutmeg; thus, the plant is commonly known as African nutmeg, calabash nutmeg or Jamaican nutmeg; and it is a large tropical tree which can reach 35 m height and 2 m in diameter [25]. It is native to tropical West Africa and further east to Uganda, Kenya and Tanzania where it grows naturally in evergreen forests but has been introduced to Jamaica, other parts of the Caribbean and elsewhere [26]. Its large leaves (35 cm long and 18 cm wide) are purple at first but turn a smooth deep green on the upper side with paler green underneath. They are prominently veined, and the petiole is purplish. The exotic, conspicuous and scented flowers hang down on long stalks and have three calyx lobes and three petals arranged in two whorls [27]. The flowers are followed by large woody fruits filled with brown seeds embedded in an aromatic pulp [25]. The medicinal uses of the seeds are to treat headaches, pains, toothaches, haemorrhoids, stomach ache, relieve constipation and control passive uterine haemorrhage in women immediately after child birth [24, 25, 28] and hypertension [25].
\nThe leaves of sacred garlic pear (Crateva adansonii) which are eaten with soups or mixed with cereal are also used medicinally in different parts of Africa and Asia [29, 30]. It belongs to the family Capparaceae and is widely distributed as a small handsome tree of the galleried forest and savannah woodland often found on river banks across Africa [29]. The species is confined to Africa but bears very close affinity to the Asian Crateva religiosa G. Forst with which it has been equated by some authorities [29]. It attains a height of 7 m or more with an irregular trunk which is seldom straight and could be cultivated for ornamental purposes due to its dense masses of white flowers borne at the ends of all the shoots [29]. Where it survives bush burning and repeated stripping of its leaves, the tree is often stunted. The wood is strong-smelling when cut and is soft and yellow [29]. In Eastern Nigeria, C. adansonii is used medicinally, its leaves being in high demand for the treatment of ear and parasitic infections [31]. The leaves are applied externally to relieve joint pains; the fresh juice from the leaves is used for the relief of ear ache, eye infection and anodyne in toothache [32]. The leaves are also used in fumigations for treating jaundice and yellow fever, applied to the head as a mild counter-irritant for easing headaches, and a steam bath of over the face is used as a remedy for all troubles due to poor vision [29]. The bark is said to be rubefacient and tonic, widely used as a remedy for stomach-troubles and used both internally and externally for treating sterility. It is used in combination with Flacourtia flavescens as a treatment for leprosy [29]. Powdered and boiled in oil, it is used as an application for rheumatic condition, and a bark paste is used as a poultice on swellings [29]. The powdered bark is used in rheumatism, itch, epilepsy, stomach troubles and asthma [33]. The powdered leaves and bark are considered to be rubefacient and are used especially on cysts. The root is used as a febrifuge and in several treatments for syphilis. The dried, ground roots are used as an application to swollen parts of the body, while the seeds have unspecified medicinal uses [29].
\nThis review identifies lesser known aromatic plants in Nigeria and current reports on their utilization, constituents and properties. The aim is to provide an insight into the health-promoting potentials of biologically active constituents of: wild ginger (Siphonochilus aethiopicus (Schweinf) B.L Burtt), African nutmeg (Monodora myristica (Gaertn) Dunal) and sacred garlic pear (Crateva adansonii DC). This is because diets rich in plant foods can provide biologically active phytochemicals that promote health [34].
The sensory perception of wild ginger depends on a variety of odorants including esters, monoterpenes, sesquiterpenes, aldehydes, pyrazines and thiophenes which are important for the mild and pleasant aroma both in the fresh and in roasted spice as against the hot/pungent flavours of ginger and other Zingiberaceae [35]. Aroma extracts dilution analysis (AEDA) employing the gas chromatography/olfactometry (GC/O) technique was reported for the organoleptic evaluation of these odorants and their odour quality together with quantification from GC-FID/GC-MS profiles [35]. Thus, the sweet/fruity ester flavours, methyl-2-/-3-methyl butanoates and derivatives of the apple flavour were reported to be the most important odorants perceived at the highest dilution of the aroma extract of the fresh spice [35]. These were followed by the monoterpene β-phellandrene which has a terpenish/woody odour and is also important for the aroma of ginger and dill [35–37]. Another sweet/fruity flavour propyl-2-methylbutanoate also an apple flavour follows before the roasty/earthy smelling 2-isopropyl-3-methoxypyrazine and 2-isobutyl-3-methoxypyrazine which are known to have a hot/paprika taste and are also present in paprika pepper and chillies [35–38]. The sesquiterpene curzerenone (sweet/coconut-like) is perceived at the next significant dilution together with the roasty/potato-like methional [35]. In the roasted sample, terpenish/woody β-phellandrene is the most important odorant followed by the roasty/earthy smelling pyrazines before the sweet/fruity flavoured butanoates. The pungent smelling principle 2-acetyl thiophene, which is absent in the fresh sample, is next followed by the sesquiterpene curzerenone (sweet/coconut-like) together with the roasty/potato-like methional [35].
\nPrincipal component analysis using GC shows that the constituents of wild ginger are mostly sesquiterpenes as against monoterpenoids or diterpenoids [16, 35, 39]. Five eudesmane sesquiterpenoids as shown in Figure 1: 4aαH-3,5α,8aβ-trimethyl-4,4a,8a,9-tetrahydronaphtho[2, 3b]-furan-8-one; 2-hydroxy-4aαH-3,5α,8aβ-trimethyl-4,4a,8a,9-tetrahydro-naphtho[2, 3b]-furan-8(5H)-one; 4aαH-3,5α,8aβ-trimethyl-4,4a,8a,9-tetrahydronaphtho-([2, 3b]-dihydrofuran-2-one)-8-one; 9aβ-hydroxy-4aαH-3,5α,8aβ-trimethyl-4,4a,8a,9-tetrahydronaphtho-([2, 3b]-dihydrofuran-2-one)-8-one and 4aαH-3,5α,8aβ-trimethyl-4,4a,8a-trihydronaphtho-([2, 3b]-dihydrofuran-2-one)-8-one were isolated as the constituents of the South African variety [16, 17]. However, the elemane sesquiterpenoids: curzerenone and epi-curzerenone, the germacrane sesquiterpenoids: furanodiene (8,12-epoxy-1(10)E,4Z,7,11-germacratetraene); isofuranodiene (8,12-epoxy-1(10)E,4Z,7,11-germacratetraene) and furanodienone (8,12-epoxy-1(10)E,4Z,7,11-germacratetraen-6-one) together with the labdane diterpenoids: 8(17),12E-labdadiene-15,16-dial, 15-hydroxy-8(17),12E-labdadiene-16-al, and 16-oxo-8(17), 12E-labdadiene-15-oic acid (zerumin A) as also shown in Figure 1 were isolated from the Nigerian variety [35, 39].
Isolated constituents of Siphonochilus aethiopicus.
A yield of 45-6g kg−1 essential oils containing 75% monoterpene hydrocarbons; the major compounds being: α-phellandrene (50–4%), α-pinene (5–5%) and myrcene (4–35%) has been reported for the African nutmeg [40]. Few sesquiterpene hydrocarbons (3%) and oxygenated compounds such as germacrene-D-4-ol (9–5%) were also reported as against another report of 25.48% germacrene-D-4-ol [41]. Meanwhile, an essential oil yield of 6.2% (dry weight basis) has also been reported [42]. Prenylated indole alkaloids are considered a chemotaxonomic marker of the genus, and 5-formyl indole and 5-(3-oxo-but-1-enyl) indole as shown in Figure 2 have been reported from Monodora myristica and other species of Monodora [21, 43, 44].
Isolated constituents of Monodora myristica.
The volatile oils of the sacred garlic pear whole plant reportedly show 43.5 and 41.1% oxygenated monoterpenes and aliphatic compounds, respectively. The major constituents are linalool (30.2%) and nonanal (17.2%), and it contains no sesquiterpene hydrocarbons [45]. The leaves are also known to have a disagreeable smell when crushed [29]. The triterpenes: oleanolic acid and 4-epi-hederagenin were isolated from the 1:1 C2H2:MeOH extract of its seed as shown in Figure 3 [46]. Then, the hexane extract of the leaf yielded the antibiotic aurantiamide acetate while the ethyl acetate extract afforded ethyl pyropheophorbide A, purpurin-18 ethyl ester and pyropheophorbide A as also shown in Figure 3 [31]. Additionally, the triterpene lupeol was also isolated from a 1:1 dichloromethane/methanol fraction of the leaf as illustrated in Figure 3 [47].
Isolated constituents from Crateva adansonii bioactivity.
It has been reported that the leaf and rhizome extracts of S. aethiopicus possess anti-microbial and anti-fungal properties [48]. However, the activities of the leaf extracts are much lower than those of the rhizome extracts which inhibited Bacillus subtilis, Micrococcus kristinae, Bacillus cereus, Staphylococcus aureus, Staphylococcus epidermidis and Klebsiella pneumoniae and showed anti-fungal properties against Aspergillus flavus, Aspergillus glaucus, Candida albicans, Candida tropicalis, Trichophyton mentagrophytes and Trichophyton rubrum [48, 49]. This is despite the similar chemical composition of the essential oils of the leaf and rhizome [20]. Again, the anti-fungal activities of some of the isolated constituents of the rhizomes and tubers: epi-curzerenone and furanodienone against Candida albicans, and 8(17),12E-labdadiene-15,16-dial against Candida tropicalis and Candida guilliermondii have been reported [50, 51]. Moderate activity of the crude rhizome extract and isolated diterpenes: 8(17),12E-labdadiene-15,16-dial and 15-hydroxy-8(17),12E-labdadiene-16-al against Mycobacterium tuberculosis has also been reported [39].
\nThe in vitro anti-proliferative properties of the essential oils of wild ginger against MCF-7 cancer cells were reported [52]; indeed, it has been suggested that the presence of antiseptic monoterpenoids contributes to its bioactivity [11]. In vitro cytotoxicity determinations of the crude rhizome extract and isolated constituents using five cell lines: SH-SY5Y, Jurkat, L929, Hep G2 and Hs 27 were also carried out [39]. Epi-curzerenone and furanodienone were inactive against the five different cell lines tested, while two of the diterpenes reportedly showed specific cytotoxic effects. 8(17),12E-Labdadiene-15,16-dial had moderate effect on the normal cell line Hs 27 and was cytotoxic to SH-SY5Y, the cancerous Jurkat and L929. However, only Jurkat and SH-SY5Y were affected by 15-hydroxy-8(17),12E-labdadiene-16-al [39].
\nThe in vitro and in vivo anti-inflammatory properties of S. aethiopicus have also been reported [53]. The rhizome extract and the isolated furanoterpenoid, 4aαH-3,5α,8aβ-trimethyl-4,4a,8a,9-tetrahydronaphtho[2, 3b]-furan-8-one, showed in vitro inhibition of glucocorticoid and histamine H1 receptor binding and phosphodiesterase IV activity [53]. OVA-sensitized and challenged mice showed significantly reduced lung inflammation and the percentage of eosinophils in bronchoalveolar lavage fluid after administration of S. aethiopicus extracts but airway hyper reactivity was not influenced supporting anecdotal accounts of effectiveness against asthma, sinusitis, colds and flu [53]. Another report on the anti-inflammatory properties of the extracts of various parts of S. aethiopicus showed that the in vitro cyclooxegenase-1 (COX-1) inhibition of the stem and leaf extracts was reportedly higher than that of the rhizome [54]. High inhibition of cyclooxygenase and hence the prostaglandin pathway which should prevent uterine contraction and relieve dysmenorrhoea was again reported for the leaves and tubers of wild ginger [55]. However, in vitro reduction of pre-contracted uterine muscle was not observed [55].
\nAdditionally, the in vitro anti-plasmodial activity for the ethanolic extracts and isolated eudesmane sesquiterpenoids of S. aethiopicus rhizomes against the chloroquine-sensitive and chloroquine resistant strains of Plasmodium falciparum has also been reported [17]. The substitution of the OH group in the sesquiterpene structure with hydrogen resulted in a threefold increase in activity against the chloroquine-resistant strain and an introduction of a double bond further improved the activity [17]. It is suggested that the anti-plasmodial activity is due to the furan moiety [17, 56]. Further in vitro anti-protozoal property of S. aethiopicus was reported against Trypanosoma brucei brucei (S427) blood stream forms by the crude rhizome extract, and it increased with the pure components: 8(17),12E-labdadiene-15,16-dial, epi-curzerenone and furanodienone [39].
\nThe crude seed extract of Monodora myristica and isolated 5-formyl indole and 5-(3-oxo-but-1-enyl)indole reportedly showed no in vitro cytotoxicity against normal PNT2A cells and no anti-trypanosomal activity against Trypanosoma brucei brucei (S427) blood stream forms [43]. There was also no in vitro cytotoxicity when the crude seed extract was tested against five different cancerous cell lines [57]. Similarly, no lethality against brine shrimp (Artemia salina) and low anti-microbial activity against the Mycobacterium species: M. madagascariense and M. indicus pranii were reported for the stem bark extract of Monodora carolinae and constituent 5-formyl indole [58]. However, some of these prenylated indole alkaloids reportedly show interesting in vitro anti-plasmodial properties against the multi-drug-resistant strain K1 of Plasmodium falciparum [59].
\nAgain, there are reports on the in vitro anti-oxidant properties and protective potential against free radicals of M. myristica seeds which suggest usage in the management of diseases associated with oxidative stress [28, 59, 60]. In vivo studies on the aqueous extracts of the seed and fruit also suggest that anti-oxidant bio-constituents play an important role in the prevention of liver toxicity possibly by inhibiting bioaccumulation of free radicals in animal models and could also reverse liver toxicity induced by high cholesterol diets and exert hypocholesterolemic effects [25, 61].
\nAlso, the crude seed extracts of M. myristica reportedly exhibit profound in vitro anti-sickling properties suggesting that the spice/extracts could be used in combination with other foods in the management and prophylactic control of sickle cell crisis [62].
\nIn vitro anti-microbial properties have been reported for C. adansonii leaf extracts against Pseudomonas aeruginosa, Escherichia coli, Salmonella typhii, Staphylococcus aureus, Klebsiella pneumoniae, Bacillus subtilis, Shigella sonei, Pasteurella pestis, Yersinia enterocolitica and anti-fungal properties against two fungi: Aspergillus niger and Candida albicans [63–65]. It has also been suggested that the traditional use of the leaves against several inflammatory diseases such as rheumatism, arthritis and gout is due to xanthine oxidase inhibition [32].
\nIn vitro anti-oxidant properties and in vivo analgesic properties have also been reported for the methanolic extracts of the stem bark [66]. The methanolic extracts of the leaves and constituent lupeol were also reported to show in vitro anti-oxidant properties [47].
\nAdditionally, there is a report on the in vitro anti-trypanosomal activity of the leaf extracts and isolated aurantiamide acetate, ethyl pyropheophorbide A, purpurin-18 ethyl ester and pyropheophorbide A against the African trypanosome Trypanosoma brucei brucei (S427) blood stream forms [31]. In silico testing of these ligands with the potential biomolecular targets of T. brucei: riboflavin kinase, trypanothione reductase, sterol-14α-demethylase, rohedsain and glutathione synthetase revealed multi-functional scaffolds validating the possibility of anti-trypanosomal activity [31].
Overall, organoleptic studies encourage the increased utilization of wild ginger, African nutmeg and sacred garlic pear to flavour foods. Moreover, a significant number of in vitro and laboratory animal studies support and explain the folk medicinal usage of these herbs and spices. These spices have anti-microbial, anti-oxidant, anti-inflammatory and in some instances anti-plasmodial and anti-cancer actions. As several metabolic diseases and age-related degenerative disorders are closely associated with oxidative processes in the body, further clinical studies on the use of these spices or their constituents as sources of anti-oxidants and anti-inflammatory agents are needed.
There may not be a precise background to the first discovery and application of phase change materials (PCMs). Perhaps, from the earliest days where human has acquired the intellect, he has realized the existence of these substances or, maybe, has used them without recognizing their nature. Throughout science and technology evolution, more precisely, since the heat capacity of materials and sensible or latent heats have been known, their ability to store and release thermal energy has also been considered. However, A. T. Waterman submitted the first report of discovery in the early 1900s. In recent years, scientists have paid particular attention to these materials, and their commercialization began from those years.
Perhaps the main reason for this attention was the problems caused by energy mismanagement and improper use of it. Today, inadequate energy management, especially fossil fuels, has caused many environmental and economic problems. Therefore, the necessity of efficient energy demand as well as development of renewable energies and energy storage systems is highly significant. One of the important topics in this field is the design of special energy storage equipment to other types. Energy storage not only reduces the discrepancy between energy supply and demand but also indirectly improves the performance of energy generation systems as well as plays a vital role in saving of energy by converting it into other reliable forms. Hence, this matter saves high-quality fuels and reduces energy wastes [1, 2, 3].
Energy storage is one of the important parts of renewable energies. Energy can be stored in several ways such as mechanical (e.g., compressed air, flywheel, etc.), electrical (e.g., double-layer capacitors), electrochemical (e.g., batteries), chemical (e.g., fuels), and thermal energy storages [4].
Among several methods of energy storage, thermal energy storage (TES) is very crucial due to its advantages. TES is accomplished by changing the internal energy of materials, such as sensible heat, chemical heat, latent heat, or a combination of them.
In sensible heat storage (SHS) systems, heat can be stored by increasing the temperature of a material. Hence, this system exploits both the temperature changes and the heat capacity of the material to store energy. The amount of heat stored in this system depends on the specific heat, temperature differences, and amount of material; thus it requires a large amount of materials, whereas Latent heat storage (LHS) is generally based on the amount of heat absorbed or released during the phase transformation of a material. Lastly, In the chemical heat storage (CHS), heat is stored by enthalpy change of a chemical reaction.
Among the aforementioned heat storage systems, the LHS is particularly noteworthy. One of the special reasons is its ability to store large amount of energy at an isothermal process [5, 6, 7].
Any high-performance LHS system should contain at least one of the following terms:
Appropriate PCM with optimum melting temperature range
Desirable and sufficient surface area proportional to the amount of heat exchange
Optimal capacity compatible with PCM
Phase change materials perform energy storage in LHS method. In this case, a material during the phase change absorbs thermal energy from surrounding to change its state, and in the reverse process, the stored energy is released to the surrounding. PCMs initially behave likewise to other conventional materials as the temperature increases, but energy is absorbed when the material receives heat at higher temperatures and close to the phase transformation. Unlike conventional materials, in PCMs absorption or release of thermal energy is performed at a constant temperature. A PCM normally absorbs and releases thermal energy 5–14 times more than other storage materials such as water or rock [8, 9].
PCMs can store thermal energy in one of the following phase transformation methods: solid-solid, solid-liquid, solid-gas, and liquid-gas. In the solid-solid phase change, a certain solid material absorbs heat by changing a crystalline, semicrystalline, or amorphous structure to another solid structure and vice versa [10]. This type of phase change, usually called phase transitions, generally has less latent heat and smaller volume change comparing to the other types. Recently, this type of PCM has been used in nonvolatile memories [11].
Solid-liquid phase change is a common type of commercial PCMs. This type of PCM absorbs thermal energy to change its crystalline molecular arrangement to a disordered one when the temperature reaches the melting point. Unlike solid-solid, solid-liquid PCMs contain higher latent heat and sensible volumetric change. Solid-gas and liquid-gas phase changes contain higher latent heat, but their phase changes are associated with large volumetric changes, which cause many problems in TES systems [8]. Although the latent heat of solid-liquid is less than liquid-gas, their volumetric change is much lower (about 10% or less). Therefore, employing PCMs based on solid-liquid phase change in TES systems would be more economically feasible.
The overall classification of energy storage systems as well as phase change materials is given in Figure 1.
Overview of energy storage and classification of phase change materials.
As mentioned in the previous section, despite the high thermal energy absorption capacity, PCMs in liquid-gas and solid-gas transitions have extremely high volume changes. On the other hand, solid-solid PCMs also have a lower thermal energy storage capacity. Therefore, the abovementioned PCMs, with the exception of specific cases, have not received much attention to commercialization. Currently, the most common type of transition that has been mass-marketed is solid-liquid PCMs. The classification of phase change materials is schematically given in Figure 1. Solid-liquid PCMs are generally classified as three general organics, inorganic, and eutectics [12, 13]. However, in some references they are classified into two major organics and inorganics.
Inorganic PCMs mainly have high capacity for thermal energy storage (about twice as much as organic PCMs) as well as have higher thermal conductivity. They are often classified as salt hydrates and metals.
Salt hydrates are the most important group of inorganic PCMs, which is widely employed for the latent heat energy storage systems. Salt hydrates are described as a mixture of inorganic salts and water (AB × nH2O). The phase change in salt hydrates actually involves the loss of all or plenty of their water, which is roughly equivalent to the thermodynamic process of melting in other materials.
At the phase transition, the hydrate crystals are subdivided into anhydrous (or less aqueous) salt and water. Although salt hydrates have several advantages, some deficiencies make restrictions in their application. One of these problems is incongruent melting behavior of salt hydrates. In this problem the released water from dehydration process is not sufficient for the complete dissolution of the salts. In this case, the salts precipitate and as a result phase separation occurs. In order to prevent this problem, an additional material such as thickener agent is added to salt hydrates. Another major problem with salt hydrates is the supercooling phenomenon. In this phenomenon, when crystallization process occurs, the nucleus formation is delayed; therefore, even at temperatures below freezing, the material remains liquid [7, 11, 14].
Overall, the most attractive properties of salt hydrate are (i) high alloy latent temperature, (ii) relatively high thermal conductivity (almost two to five times more than paraffin), and (iii) small volume changes in melting. They are also very low emitting and toxic, adaptable to plastic packaging, and cheap enough to use [15].
Metalsare another part of the inorganic PCMs. Perhaps the most prominent advantages of metals are their high thermal conductivity and high mechanical properties. Metals are available over a wide range of melting temperatures. They are also used as high-temperature PCMs.
Some metals such as indium, cesium, gallium, etc. are used for low-temperature PCMs, while others such as Zn, Mg, Al, etc. are used for high temperatures. Some metal alloys with high melting points (in the range of 400–1000°C) have been used for extremely high temperature systems. These metal alloys as high-temperature PCMs can be used in the field of solar power systems [16, 17]. They can also be used in industries that require temperature regulation in furnaces or reactors with high operating temperatures.
Perhaps the most important fragment is the organic PCMs. Organic PCMs show no change in performance or structure (e.g., phase separation) over numerous phase change cycles. In addition, supercooling phenomena cannot be observed in organic PCMs. The classification of organic PCMs is unique. This division is mainly based on their application contexts. In general, they are classified into two major paraffin and non-paraffin sections.
Paraffins are the most common PCMs. Since this book is about paraffin, to avoid duplication, this section will briefly discuss the chemistry (structure and properties) of paraffin, but their ability as phase change materials will be reviewed in detail.
Non-paraffinic organic PCMs are known to be the most widely used families. In addition to their different properties compared to paraffins, they have very similar properties to each other. Researchers have used various types of ether, fatty acid, alcohol, and glycol as thermal energy storage materials. These materials are generally flammable and less resistant to oxidation [18, 19, 20].
Although non-paraffin organic PCMs have high latent heat capacity, they have weaknesses such as flammability, low thermal conductivity, low combustion temperatures, and transient toxicity. The most important non-paraffinic PCMs are fatty acids, glycols, polyalcohols, and sugar alcohols.
Fatty acids [CH3(CH2)2nCOOH] also have high latent heat. They can be used in combination with paraffin. Fatty acids exhibit high stability to deformation and phase separations for many cycles and also crystallize without supercooling. Their main disadvantages are their costs. They are 2–2.5 times more expensive than technical grade paraffins. Unlike paraffins, fatty acids are of animal or plant origin. Their properties are similar to those of paraffins, but the melting process is slower. On the other hand, they are moderately corrosive as well as generally odorous [21].
A eutectic contains at least two types of phase change materials. Eutectics have exceptional properties. In eutectics, the melting-solidification temperatures are generally lower than the constituents and do not separate into the components through the phase change. Therefore, phase separation and supercooling phenomena are not observed in these materials.
Eutectics typically have a high thermal cycle than salt hydrates. Inorganic-inorganic eutectics are the most common type of them. However, in recent studies, organic-inorganic and organic-organic varieties have received more attention. The major problem of eutectics is their commercialization. Their cost is usually two to three times higher than commercial PCMs [22, 23].
Some of the above PCMs and their thermal properties, which are competitive with paraffins in terms of latent heat capacity, are summarized in Table 1.
Type of PCMs | Materials | Melting point (°C) | Latent heat (kJ/kg) | Density* (kg/m3) | Thermal conductivity (W/mK)** | Ref. | |
---|---|---|---|---|---|---|---|
Inorganic salt hydrates | LiClO3·3H2O | 8 | 253 | 1720 | [24, 25] | ||
K2HPO4·6H2O | 14 | 109 | [24] | ||||
Mn(NO3)2·6H2O | 25.8 | 126 | 1600 | [14, 25] | |||
CaCl2·6H2O | 29.8 | 191 | 1802 | 1.08 | [24, 25] | ||
Na2CO3·10H2O | 32–34 | 246–267 | [14, 24] | ||||
Na2SO4·10H2O | 32.4 | 248, 254 | 1490 | 0.544 | [14, 26] | ||
Na2HPO4·12H2O | 34–35 | 280 | 1522 | 0.514 | [15, 26] | ||
FeCl3·6H2O | 36–37 | 200, 226 | 1820 | [25, 26] | |||
Na2S2O3·5H2O | 48–49 | 200, 220 | 1600 | 1.46 | [15, 26] | ||
CH3COONa·3H2O | 58 | 226, 265 | 1450 | 1.97 | [15, 26] | ||
Non-paraffinic organic PCMs | Fatty acids | Formic acid | 8.3 | 247 | 1220 | — | [1, 25] |
n-Octanoic acid | 16 | 149 | 910 | 0.148 | [21, 27] | ||
Lauric acid | 43.6 | 184.4 | 867 | [21, 25] | |||
Palmitic acid | 61.3 | 198 | 989 | 0.162 | [21, 27] | ||
Stearic acid | 66.8 | 259 | 965 | 0.172 | [21, 25] | ||
Polyalcohols | Glycerin | 18 | 199 | 1250 | 0.285 | [1, 25] | |
PEG E600 | 22 | 127.2 | 1126 | 0.189 | [27] | ||
PEG E6000 | 66 | 190 | 1212 | [27] | |||
Xylitol | 95 | 236 | 1520 | 0.40 | [28] | ||
Erythritol | 119 | 338 | 1361 | 0.38 | [28] | ||
Others | 2-Pentadecanone | 39 | 241 | [1, 25] | |||
4-Heptadekanon | 41 | 197 | [1, 25] | ||||
D-Lactic acid | 52–54 | 126, 185 | 1220 | [1, 25] | |||
Eutectics | O-O, O-I, I-I *** | CaCl2·6H2O + MgCl2·6H2O | 25 | 127 | 1590 | [27] | |
Mg(NO3)2·6H2O + MgCl2·6H2O | 59 | 144 | 1630 | 0.51 | [27] | ||
Trimethylolethane + urea | 29.8 | 218 | [21] | ||||
CH3COONa·3H2O + Urea (60:40) | 31 | 226 | [27] | ||||
Metals | Mg-Zn (72:28) | 342 | 155 | 2850 | 67 | [16, 17] | |
Al-Mg-Zn (60:34:6) | 450 | 329 | 2380 | [16, 17] | |||
Al-Cu (82:18) | 550 | 318 | 3170 | [16, 17] | |||
Al-Si (87.8:12.2) | 580 | 499 | 2620 | [16, 17] |
Thermophysical properties of some common PCMs with high latent heat.
At 20°C.
Just above melting point (liquid phase).
Inorganic-inorganic (I-I), organic-inorganic (O-I), and organic-organic (O-O).
Paraffin is usually a mixture of straight-chain n-alkanes with the general formula CH3-(CH2)n-CH3. However, in some cases, paraffin is used as another name for alkanes. Gulfam R. et al. in their article have classified paraffins based on the number of carbon atoms as well as their physical states. According to this classification, at room temperature, 1–4 numbers of carbons refer to pure alkanes in a gas phase, 5–17 carbons are liquid paraffins, and more than 17 is known as solid waxes. These waxy solids refer to a mixture of saturated hydrocarbons such as linear, iso, high branched, and cycloalkanes [29]. Generally, paraffin-based PCMs are known as waxy solid paraffins. Commercial paraffins contain mixture of isomers, and therefore, they have a range of melting temperatures.
Paraffins typically have high latent heat capacity. If the length of the chain increases, the melting ranges of waxes also increase, while the latent heat capacity of melting is not subject to any particular order (Table 2).
Materials | Melting point (°C) | Latent heat (kJ/kg) | Density* (kg/m3) | Thermal conductivity** (W/mK) |
---|---|---|---|---|
n-Tetradecane (C14) | 6 | 228–230 | 763 | 0.14 |
n-Pentadecane (C15) | 10 | 205 | 770 | 0.2 |
n-Hexadecane (C16) | 18 | 237 | 770 | 0.2 |
n-Heptadecane (C17) | 22 | 213 | 760 | 0145 |
n-Octadecane (C18) | 28 | 245 | 865 | 0.148 |
n-Nonadecane (C19) | 32 | 222 | 830 | 0.22 |
n-Eicosane (C20) | 37 | 246 | ||
n-Henicosane (C21) | 40 | 200, 213 | 778 | |
n-Docosane (C22) | 44.5 | 249 | 880 | 0.2 |
n-Tricosane (C23) | 47.5 | 232 | ||
n-Tetracosane (C24) | 52 | 255 | ||
n-Pentacosane (C25) | 54 | 238 | ||
n-Hexacosane (C26) | 56.5 | 256 | ||
n-Heptacosane (C27) | 59 | 236 | ||
n-Octacosane (C28) | 64.5 | 253 | ||
n-Nonacosane (C29) | 65 | 240 | ||
n-Triacontane (C30) | 66 | 251 | ||
n-Hentriacontane (C31) | 67 | 242 | ||
n-Dotriacontane (C32) | 69 | 170 | ||
n-Triatriacontane (C33) | 71 | 268 | 880 | 0.2 |
Paraffin C16-C18 | 20–22 | 152 | ||
Paraffin C13-C24 | 22–24 | 189 | 900 | 0.21 |
RT 35 HC | 35 | 240 | 880 | 0.2 |
Paraffin C16-C28 | 42–44 | 189 | 910 | |
Paraffin C20-C33 | 48–50 | 189 | 912 | |
Paraffin C22-C45 | 58–60 | 189 | 920 | 0.2 |
Paraffin C21-C50 | 66–68 | 189 | 930 | |
RT 70 HC | 69–71 | 260 | 880 | 0.2 |
Paraffin natural wax 811 | 82–86 | 85 | 0.72 (solid) | |
Paraffin natural wax 106 | 101–108 | 80 | 0.65 (solid) |
In general, paraffin waxes are safe, reliable, inexpensive, and non-irritating substances, relatively obtained in a wide range of temperatures. As far as economic issues are concerned, most technical grade waxes can be used as PCMs in latent heat storage systems. From the chemical point of view, paraffin waxes are inactive and stable. They exhibit moderate volume changes (10–20%) during melting but have low vapor pressure.
The paraffin-based PCMs usually have high stability for very long crystallization-melting cycles. Table 2 illustrates the thermal properties of some paraffin waxes.
Besides the favorable properties, paraffins also show some undesirable properties such as low thermal conductivity, low melting temperatures, and moderate-high flammability. Some of these disadvantages especially thermal conductivity and flammability can be partially eliminated with the help of additives or paraffin composites.
Measures must be taken to make the solid-liquid PCMs usable. For this purpose, there are several methods for stabilizing the shapes of paraffinic PCMs. Two main methods of them are discussed below.
Encapsulation is generally a worthy method to protect and prevent leakage of PCMs in the liquid state. The capsules consist of two parts, the shell and the core. The core part contains PCMs, whereas the shell part is usually composed of polymeric materials with improved mechanical and thermal properties. The shell part plays the role of protection, heat transfer, and sometimes preventing the release of toxic materials into the environment. In these cases, the shell must have appropriate thermal conductivity. Polymeric shells are also commonly used in encapsulating PPCMs. The choice of core part depends on its application field. The encapsulation of PPCMs is classified into three major parts: bulk or macroencapsulation, microencapsulation, and nano-encapsulation.
Macroencapsulation is one of the simplest ways to encapsulate paraffins. This method has a lower cost than other methods. These products are used in transportation, buildings, solar energy storage systems, and heat exchangers. Sometimes metals are also used as shell materials [30].
In order to increase the efficiency of heat transfer in these types of capsules, either the size of the capsules should be appropriately selected or suitable modifiers should be used. In general, the smaller the diameter of spherical capsules or cylinders, the better the heat transfer. In some cases, metal foams are used to improve the heat transfer properties of paraffin. Aluminum and copper open-cell foams are among the most studied, whereas, in other cases metal oxides, metals and graphite are used [30, 31].
There are various forms of macroencapsulation, such as ball shape, spherical shape, cylindrical, flat sheets, tubular, etc. [31]. Cylindrical tubes are one of the famous forms of macroencapsulated PPCMs. This type of encapsulation is most commonly used in buildings or in solar energy storage systems.
Most of the research carried out on macroencapsulated PPCMs has been focused on improving their thermal conductivity. In one of these studies, different metal oxide nanoparticles such as aluminum oxide, titanium oxide, silicon oxide, and zinc oxide were used to improve the thermal conductivity of paraffin. The results show that titanium oxide performs better under the same conditions than the other oxides [32]. In a similar study, copper oxide nanoparticles were used to improve thermal conductivity and performance of paraffin in solar energy storage systems [33]. In some studies, graphite flakes and expanded graphite have also been used as improving agent for heat conductivity [31].
Hong et al. have used polyethylene terephthalate pipes as a shell for paraffin. In this macroencapsulated system, introduced as cylinder modules, float stone has been added to paraffin as an enhancer of thermal conductivity. In this study, the effect of various parameters such as pipe diameter on heat transfer is investigated, and the results of experimental section are compared with modeling [34].
D. Etansova et al. studied numerical computation and heat transfer modeling of paraffin-embedded stainless steel macroencapsulates for use in solar energy storage systems. In this study, the effect of geometric size and shape on heat transfer was investigated [35].
Microencapsulation of PCMs is another suitable way to improve efficiency and increase thermal conductivity. The size of the microencapsulates usually ranges from 1 μm to 1 mm. Microencapsulation of paraffins is a relatively difficult process, but it performs better than macroencapsulates. This is due to increased contact surface area, shorter discharge and loading times, and improved thermal conductivity. Different materials are used for the shell part of the microencapsulates.
In general, there are two major physical and chemical methods for microencapsulation. The most important physical methods are fluidized bed, spray dryer, centrifuge extruder, and similar processes. However, chemical methods are often based on polymerization. The most important techniques include in situ suspension and emulsion polymerization, interfacial condensation polymerization, and sol-gel method. The latter is sometimes known as the physicochemical method [12, 29].
In the suspension or emulsion polymerization method, the insoluble paraffin is first emulsified or suspended in a polar medium, which is predominantly aqueous phase, by means of high-speed stirring. Surfactants are used to stabilize the particles. Then, lipophilic monomers are added to the medium, and the conditions are prepared for polymerization. This polymer, which is insoluble in both aqueous and paraffin phases, is formed on the outer surface of paraffin particles and finally, after polymerization, encapsulates the paraffin as a shell. The size of these capsules depends on the size of emulsion or suspension of paraffin droplets. Sometimes certain additives are added to the medium to improve some of the polymer properties. For instance, in some studies, polyvinyl alcohol (PVA) has been added to the medium with methyl-methacrylate monomer, which is known as one of the most important shell materials. As a result, paraffin has been encapsulated by PVA modified polymethyl methacrylate (PMMA). Adding this modifier forms a smooth surface of the microencapsulates [36, 37].
In the interfacial method, soluble monomers in the organic phase with other monomers in the aqueous phase at the droplet interface form a polymer that precipitates on the outer layer of the organic phase.
The sol-gel method is a multi-step procedure. In this method, firstly, an organosilicon compound such as tetraethoxysilane (TEOS) is hydrolyzed in an acidic medium at low pH. The prepared homogenous solution is known as the sol part. Then, the paraffin emulsion is prepared in an aqueous medium and stabilized by special emulsifiers. Actually, these emulsifiers are the first layer of the shell. Subsequently, the sol solution is slowly added to the aqueous phase containing paraffin. The silicon compounds containing OH groups (silanols) form hydrogen bonding with polar side of emulsifiers, and finally the condensation process is carried out on the first layer interface. As a result, paraffin microencapsulates with an inorganic material that is often silica. Silica is one of the significant materials used as a shell for micro and nano-encapsulation. Silica has high thermal conductivity and on the other hand has better mechanical properties than some polymers [38, 39, 40, 41].
As mentioned, most of the materials used to microencapsulation are polymers. The main polymers used as shell materials are polymethyl methacrylate [42], polystyrene [43], urea-formaldehyde [44], urea-melamine-formaldehyde [45], polyaniline [46], etc. However, in many cases, these polymers are used in modified form. For example, polymethyl methacrylate modified with polyvinyl alcohol or with other methacrylates [36, 37], polystyrene copolymers [47], and melamine modified-formaldehyde with methanol [48] can be considered. Table 3 shows the most common polymers used as shell materials.
Core material PPCM | Shell material | Encapsulation method | Particle size (μm) | Recommended application | Ref |
---|---|---|---|---|---|
n-Nonadecane | Polymethyl methacrylate | Emulsion | ~ 8 | Smart building and textiles | [42] |
n-Heptadecane | Polystyrene | Emulsion | <2 | General fields | [43] |
Commercial paraffin wax | Polystyrene-co-PMMA | Suspension | ~ 20 | [50] | |
Commercial RT21 | PMMA | Suspension | 20–40 | [36] | |
Commercial RT21 | PMMA modified with PVA | Emulsion | 15 | Building | [37] |
Commercial paraffin wax | Polyaniline | Emulsion | <1 | [46] | |
Commercial paraffin wax | Urea-formaldehyde | In situ | ~ 20 | [44] | |
n-Octadecane, n-nonadecane | Urea-melamine-formaldehyde | In situ | 0.3-0.6 | [45] | |
Commercial paraffin wax | Methanol-melamine-formaldehyde | In situ | 10–30 | Building | [48] |
Commercial paraffin wax | Silica | Sol-gel | 4–10 | Textile | [38] |
Commercial paraffin wax | Silica | Sol-gel | 0.2–0.5 | [39] | |
n-Octadecane | Silica | Sol-gel | 7–16 | [40] | |
n-Pentadecane | Silica | Sol-gel | 4–8 | [41] |
Common materials for microencapsulation of PPCMs.
In addition to the aforementioned microencapsulation approaches, which mainly form polymeric materials as shells, other materials have been also recommended. For example, Singh and colleagues have used silver metal as a shell for paraffin microencapsulates. They first emulsified paraffin into small particles in water and then converted silver salts to metallic silver via an in situ reduction reaction. The average particle size of 329 μm has been reported, and the thermal properties of paraffin have been investigated using DSC and TGA. This type of metal shell microencapsulates has been suggested for use in microelectronics heat management systems [49].
There are several techniques to study the properties of micro and nano-encapsulates. In all studies, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) have been used to determine the thermal properties of PPCMs, such as enthalpy of fusion, melting temperature, weight loss, degradation, etc. Various methods such as XRD, FTIR, and 12C NMR have been used to study the structure and chemical composition of PPCMs. The morphology and diameters of the microcapsules have often been studied by scanning electron microscopy (SEM) and particle size analyzer.
The latter technique is used to study the influence of different variables on the diameter of the microcapsules. One of these variables is the effect of stirring speed on emulsification of paraffin. The results of some studies show that higher stirring speed of emulsification process leads to decrease of the mean size of paraffin droplets [48].
Along with studies on the type of microcapsules, many studies have been conducted to improve thermal conductivity and mechanical properties of microencapsulates. Part of these studies has been dedicated to the effect of graphene and graphene oxide on the improvement of thermal conductivity [51]. L. Zhang et al. investigated the effect of graphene oxide on improving the mechanical properties and leakage protection as well as improving the thermal conductivity of melamine-formaldehyde as shell materials of PPCM microencapsulates [52]. In another part of studies, metals and metal oxides have been used. For example, 10 and 20 wt% of nanomagnetite (Fe3O4) with particle size from 40 to 75 nm increase the thermal conductivity by 48 and 60%, respectively [53]. Also, addition of TiO2 and Al2O3 nanoparticles in a mass fraction of 5% with respect to PPCM at the size range of 30–60 nm increases the thermal conductivity by 40 and 65%, respectively [54].
Nano-encapsulation of PPCM is very similar to the microencapsulation process. However, these types of encapsulation specific techniques, such as ultrasonic, are used to adjust the size of the paraffin droplets to less than 1 micron. In the next step, using the chemical methods mentioned in the microencapsulation method, the shell formation is performed. The most common method for nano-encapsulation is the emulsion polymerization method. However, although limited, interfacial and sol-gel methods have also been reported.
In recent years, research on polymeric matrix-based shape-stable PCMs has gained great importance. Among these types of phase change materials, the paraffin-polymer composite is particularly attractive. The combination of paraffin and polymers as new PCMs with a unique controllable structure can be widely used. This compound remains solid at paraffin melting point and even above without any softening, which is why this type of PCM is called shape-stable. These materials are well formed and have high-energy absorption capacity; hence they can be widely used as stable PCMs with specific properties. On the other hand, some problems such as high cost and difficulty of encapsulating processes could be resolved. Despite these advantages, some common disadvantages such as low thermal stability, low thermal conductivity, and relatively high flammability can restrict their application, particularly in building materials. For this reason, further studies are required to eliminate these disadvantages and improve the properties of these materials. A large part of research is relevant to increase or improve their thermal conductivity, flame retardation, and thermophysical and mechanical properties. Suitable additives are proposed to improve these properties [55, 56].
In some articles, a simple method involves mixing-melting of polyethylene and paraffin, consequently cooling the composite, or using a simple twin extruder to prepare a shape-stable PCM has been reported [57, 58]. When this compound contains sufficient polymer, a homogeneous mixture remains solid at temperatures above the melting point of paraffin and below the polymer melting point. During the preparation of these composites, no chemical reaction or chemical bonds are formed between the polymers and paraffin; therefore these types of compounds are considered as physical mixtures. Shape-stable PPCMs can be used in all previously described areas. Due to the thermoplastic properties of these composites, it is possible to melt and crystalize them for many cycle numbers. Shape-stable PPCMs have several advantages over other PCMs. They are also nontoxic and do not require high-energy consumption during production process.
Inaba and Tu [59] developed a new type of shape-stable PPCM and determined their thermophysical properties. These materials can be used without encapsulation. Feldman et al. [60] prepared plates of shape-stable PCM and determined their high thermal energy storage capacity when used in small chambers. In this type of polymer-based plates, fatty acids are used as PCMs that absorb or releases large amounts of heat during melting and solidification, without altering the composition of the shape-stable PCM. The same researchers determined the role of polymer-PCM sheets in stabilizing the shape and size of the plates when PCM was liquefied. The composition of paraffin and high-density polyethylene (HDPE) has been studied by Lee and Choi [61] and has been introduced as a shape-stable energy storage material. In this study, the amount of energy stored by the mentioned composites is also studied. They also studied the morphology of the high-density polyethylene crystal lattice (HDPE) and its effect on paraffin through scanning electron microscopy and optical microscopy (OM) analysis. On the other hand, they also reported of high thermal energy storage capacity of the prepared paraffin/HDPE-based shape-stable PCMs. Hong and Xin-Shi [62] synthesized polyethylene-paraffin as a shape-stable PCM and characterized its morphology and structure by scanning electron microscopy and its latent heat of melting by differential scanning calorimetry. In this study, a composition consisting of 75% paraffin as a cheap, effective, easy-to-prepare, low-temperature shape-stable PPCM is recommended. In another study, Xiao et al. [63] prepared a shape-stable PCM based on the composition of paraffin with a thermoplastic elastomer (styrene butadiene rubber) and determined its thermal properties. The obtained results show that the stable mixture has the phase changing property and the amount of latent heat of melting stored in this compound is estimated to be 80% of pure paraffin. In another part of this study, the thermal conductivity of PCMs was significantly increased by using graphite.
Despite the above benefits, some disadvantages of shape-stable PPCMs are also reported. One of the major problems is the softening and paraffin leakage phenomenon at elevated temperatures. Seiler partly resolved this problem by adding a different ratio of silica and copolymers to the polyethylene-paraffin composition [64]. Another problem is the low thermal conductivity of the polyethylene-paraffin compound. A lot of research has been conducted to increase this property. A. Sari [65] prepared two types of paraffin with different melting temperatures (42–44°C and 56–58°C) and combined each with HDPE as phase modifier. By addition of 3% expanded graphite, the thermal conductivity of composites increased by 14 and 24%, respectively. Zhang et al. [66] developed new PCMS based on graphite and paraffin with high thermal energy storage capacity and high thermal conductivity. Zhang and Ding et al. [67] have used various additives such as diatomite, Wollastonite, organic modified bentonite, calcium carbonate, and graphite to improve the thermal conductivity of shape-stable PCMs.
It should be noted that metal particles and metal oxides due to their higher thermal conductivity are widely used to improve this property of PCMs. One of the materials that has received more attention in recent years is alumina. Aluminum oxide nanoparticles were added to paraffin to increase its thermal conductivity in both liquid and solid states [57, 68]. This compound coupled with its high thermal conductivity is cheaper and more abundant than other metal oxides.
Another problem with shape-stable PPCMs is their flammability. The effect of various additives has been studied by scientists to eliminate this problem. One of the most effective of these substances is halogenated compounds, but they cause environmental pollution and also release toxic compounds while burning. Researchers have used hybrid and environmentally friendly materials to enhance the durability of flame retardant materials. They studied the effect of clay nanoparticles and organo-modified montmorillonite. Adding these materials not only increases their resistance to burning but also increases their mechanical and thermal properties [69, 70, 71]. In another study, Y. Cai et al. added paraffin, HDPE, and graphite, then added ammonium polyphosphate and zinc borate separately, and studied their resistance to burning. The results show that the addition of ammonium polyphosphate decreases flammability, while zinc borate increases the flammability risk [72]. One of the most interesting and harmless fire retardant compounds is metal hydroxides, especially aluminum hydroxide, magnesium hydroxide, or their combination [73, 74, 75].
Some researchers have used other advanced materials as supporting materials to prepare shape-stable PPCMs instead of using the polymer matrix [76, 77, 78]. Rawi et al. used acid-treated multi-walled carbon nanotubes (A-CNT). They reported that adding 5% by weight A-CNT to paraffin decreases 25% of the latent heat while increasing heat conductivity up to 84% [79]. Y. Wan et al. used pinecone biochar as the supporting matrix for PCMs. They prepared shape-stable PCM materials at different ratios and studied the leakage behavior. The optimal ratio is suggested as 60% of the PCM. For the above ratio, no PCM leakage was observed after the melting temperature. The results showed that the thermal conductivity of the same ratio shape-stable PCM increased by 44% compared to the pure PCM [80].
PCMs are available in a wide range of desired temperature ranges. Obviously, a PCM may not have all the properties required to store heat energy as an ideal material. Therefore, it would be more appropriate to use these materials in combination with either other PCMs or various additives to achieve the required features. However, as latent heat storage materials, while using PCMs, the thermodynamic, kinetic, and chemical properties as well as the economic and availability issues of them must be taken into account. Employed PCMs must have the optimum phase change temperature. On the other hand, the higher the latent heat of the material, the lower its physical size. High thermal conductivity also helps to save and release energy. From the physical and kinetic point of view, the phase stability of PCMs during melting and crystallization contributes to optimum thermal energy storage. Their high density also enables high storage at smaller material sizes. During phase change, smaller volume changes and lower vapor pressures are appropriate for continuous applications.
H. Nazir et al. in their review article [12] have explained the criteria for selection of PCMs as a pyramid. In this pyramid, at the bottom, known as the fundamentals, there are several items such as cost, regularity compliance, and safety. In the next section, the thermophysical properties such as energy storage capacity and runtime are discussed. In the upper section, reliability and operating environment consist of degradation, cycle life, shelf life, and thermal limits are reflected. Finally, at the top section of pyramid, user perception and convenience are located. These criteria help us to find a proper PCM for certain application fields.
These criteria may also be extended to paraffinic PCMs. Nowadays, paraffinic PCMs (PPCMs) are widely used as thermal energy storage materials, including solar energy storage systems, food industries, medical fields, electrical equipment protection, vehicles, buildings, automotive industries, etc. [24, 29, 81, 82, 83, 84, 85].
Generally, application fields of PPCMs can be considered in two main sections: thermal protection and energy storage purposes. The major difference between these two areas of application is in thermal conductivity of the PPCMs.
Protection and transportation of temperature-sensitive materials is one the mentioned area. Sometimes a certain temperature is required to transport sensitive medicines, medical equipment, food, etc. In all cases, using of PPCMs would be appropriate as they can regulate and stabilize the temperature over a given range. Similarly, in sensitive electrical equipment, these materials are also essential to prevent the maximum operating temperature. On the other hand, they can be used to prevent possible engine damage at high temperatures [86, 87].
One of the studies related to these issues is the use of paraffin containing heavy alkanes to protect electronic devices against overheating. In this study, paraffin has been used as a protective coating for the resistor chip, and its effect on cooling of the devices has been investigated. Experimental results show that paraffin coating increases the relative duration of overheating by 50 to 150% over the temperature range of 110–140°C [88]. In another study, a mixture of paraffin and polypropylene has been used as an overheating protector in solar thermal collectors [89].
However, energy storage purposes are the most important part of PPCM application. In general, PCMs act as passive elements and therefore do not require any additional energy source. Most studies on the application of energy storage properties of PPCMs have been confined to buildings, textiles, and solar systems. In the following, building applications will be further attended.
One of the main drawbacks of lightweight building materials is their low thermal storage capacity, which results in extensive temperature fluctuations as a result of intense heating and cooling. Therefore, PPCMs have been used in buildings due to their ability to regulate and stabilize indoor temperatures at higher or lower outdoor temperatures [90].
Generally, PPCMs in buildings are used as thermal energy storage at daytime peak temperature, and they released the stored energy at night when temperatures are low. The result of this application is to set the comfort condition for a circadian period. This application minimizes the amount of energy consumed for cooling during the day and warming up at night.
In contrast, in order to stabilize the ambient conditions at low temperatures, some special PCMs are also used in air conditioner systems. In this case, cool air is stored during the night and released into the warm hours of the day.
Y. Cui et al. [91] in a review article categorized PPCM application methods based on their location of use such as PCMs in walls, floor heating systems, ceiling boards, air-based solar heating systems, free cooling systems (with ventilation systems), and PCM shutter (in windows). Both types of encapsulation and shape-stable PPCMs could be used in all of the above classification of building applications. Sometimes these materials can be added directly to concrete, gypsum, etc. [90, 92, 93, 94, 95].
In order to increase the performance of PPCMs in this application field, great deals of studies have also been done on improving their thermal conductivity. On the other hand, extensive research into safety issues has been done to reduce the flammability of PPCMs by adding flame retardants to these materials.
Overall, these studies cover the importance of using PPCMs in heating and cooling as well as indicate the general characteristics, advantages, and disadvantages of these materials used for thermal storage in buildings.
It is clear that at this time, where renewable energy is particularly important, the use of PPCMs is on the rise. As it has been mentioned, PPCMs have many application fields due to their advantages. For example, they can be used in the construction, pharmaceutical and medical industries, textiles, automobiles, solar power systems, transportation, thermal batteries, heat exchangers, and so on.
This chapter of the book has attempted to focus more on how to use paraffins. For this reason, two methods, namely, encapsulation and shape-constant, have been widely discussed. In addition, improving their weak properties such as thermal conductivity and flammability has also been studied. Depending on the benefits of paraffins, new applications are suggested every day. Extensive studies are underway on other new applications in recent years.
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