Thermophysical properties of some common PCMs with high latent heat.
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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
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\r\n\tLiquid atomization, sprays, and fuel injection are at the heart of many chemical-reaction based propulsion and electric energy production such as internal combustion reciprocation, gas turbine and liquid rocket engines. It is known that both performance and emission of pollutants from such systems are heavily influenced by details of the fuel sprays generated from the fuel nozzles or injectors. For these reasons there has been an increasing number of R&D works targeted towards generation of fuel sprays with a desired characteristics to “match” the environment into which they are injected and subsequently burned. Such research efforts span from injector designs to spray characterization and dynamics using both experimental and modeling/simulation approaches. Therefore, the main goal of this book is to cover important advances in this field for the past fifteen years.
",isbn:null,printIsbn:null,pdfIsbn:null,doi:null,price:0,priceEur:null,priceUsd:null,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"75b0dec3efac377c1039e886e1cdbb45",bookSignature:"",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/8265.jpg",keywords:"Cylindrical Liquid Jets, Liquid Sheets, Injector Designs, Spray Characteristics, Injector Deposit Issues, Fuel Nozzle Designs, Spray Characteristics, Interaction in Combustors, Injector Designs, Spray Characteristics, Inside -Fuel Injector ,Outside Fuel Injector",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"June 14th 2018",dateEndSecondStepPublish:"July 5th 2018",dateEndThirdStepPublish:"September 3rd 2018",dateEndFourthStepPublish:"November 22nd 2018",dateEndFifthStepPublish:"January 21st 2019",remainingDaysToSecondStep:"3 years",secondStepPassed:!0,currentStepOfPublishingProcess:1,editedByType:null,kuFlag:!1,biosketch:null,coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:null,coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"11",title:"Engineering",slug:"engineering"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"270935",firstName:"Rozmari",lastName:"Marijan",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/270935/images/7974_n.png",email:"rozmari@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review, to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. Whether that be identifying an exceptional author and proposing an editorship collaboration, or contacting researchers who would like the opportunity to work with IntechOpen, I establish and help manage author and editor acquisition and contact."}},relatedBooks:[{type:"book",id:"1591",title:"Infrared Spectroscopy",subtitle:"Materials Science, Engineering and Technology",isOpenForSubmission:!1,hash:"99b4b7b71a8caeb693ed762b40b017f4",slug:"infrared-spectroscopy-materials-science-engineering-and-technology",bookSignature:"Theophile Theophanides",coverURL:"https://cdn.intechopen.com/books/images_new/1591.jpg",editedByType:"Edited by",editors:[{id:"37194",title:"Dr.",name:"Theophanides",surname:"Theophile",slug:"theophanides-theophile",fullName:"Theophanides Theophile"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3161",title:"Frontiers in Guided Wave Optics and Optoelectronics",subtitle:null,isOpenForSubmission:!1,hash:"deb44e9c99f82bbce1083abea743146c",slug:"frontiers-in-guided-wave-optics-and-optoelectronics",bookSignature:"Bishnu Pal",coverURL:"https://cdn.intechopen.com/books/images_new/3161.jpg",editedByType:"Edited by",editors:[{id:"4782",title:"Prof.",name:"Bishnu",surname:"Pal",slug:"bishnu-pal",fullName:"Bishnu Pal"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3092",title:"Anopheles mosquitoes",subtitle:"New insights into malaria vectors",isOpenForSubmission:!1,hash:"c9e622485316d5e296288bf24d2b0d64",slug:"anopheles-mosquitoes-new-insights-into-malaria-vectors",bookSignature:"Sylvie Manguin",coverURL:"https://cdn.intechopen.com/books/images_new/3092.jpg",editedByType:"Edited by",editors:[{id:"50017",title:"Prof.",name:"Sylvie",surname:"Manguin",slug:"sylvie-manguin",fullName:"Sylvie Manguin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"371",title:"Abiotic Stress in Plants",subtitle:"Mechanisms and Adaptations",isOpenForSubmission:!1,hash:"588466f487e307619849d72389178a74",slug:"abiotic-stress-in-plants-mechanisms-and-adaptations",bookSignature:"Arun Shanker and B. 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:"72",title:"Ionic Liquids",subtitle:"Theory, Properties, New Approaches",isOpenForSubmission:!1,hash:"d94ffa3cfa10505e3b1d676d46fcd3f5",slug:"ionic-liquids-theory-properties-new-approaches",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/72.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"314",title:"Regenerative Medicine and Tissue Engineering",subtitle:"Cells and Biomaterials",isOpenForSubmission:!1,hash:"bb67e80e480c86bb8315458012d65686",slug:"regenerative-medicine-and-tissue-engineering-cells-and-biomaterials",bookSignature:"Daniel Eberli",coverURL:"https://cdn.intechopen.com/books/images_new/314.jpg",editedByType:"Edited by",editors:[{id:"6495",title:"Dr.",name:"Daniel",surname:"Eberli",slug:"daniel-eberli",fullName:"Daniel Eberli"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"57",title:"Physics and Applications of Graphene",subtitle:"Experiments",isOpenForSubmission:!1,hash:"0e6622a71cf4f02f45bfdd5691e1189a",slug:"physics-and-applications-of-graphene-experiments",bookSignature:"Sergey Mikhailov",coverURL:"https://cdn.intechopen.com/books/images_new/57.jpg",editedByType:"Edited by",editors:[{id:"16042",title:"Dr.",name:"Sergey",surname:"Mikhailov",slug:"sergey-mikhailov",fullName:"Sergey Mikhailov"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1373",title:"Ionic Liquids",subtitle:"Applications and Perspectives",isOpenForSubmission:!1,hash:"5e9ae5ae9167cde4b344e499a792c41c",slug:"ionic-liquids-applications-and-perspectives",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/1373.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"2270",title:"Fourier Transform",subtitle:"Materials Analysis",isOpenForSubmission:!1,hash:"5e094b066da527193e878e160b4772af",slug:"fourier-transform-materials-analysis",bookSignature:"Salih Mohammed Salih",coverURL:"https://cdn.intechopen.com/books/images_new/2270.jpg",editedByType:"Edited by",editors:[{id:"111691",title:"Dr.Ing.",name:"Salih",surname:"Salih",slug:"salih-salih",fullName:"Salih Salih"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"872",title:"Organic Pollutants Ten Years After the Stockholm Convention",subtitle:"Environmental and Analytical Update",isOpenForSubmission:!1,hash:"f01dc7077e1d23f3d8f5454985cafa0a",slug:"organic-pollutants-ten-years-after-the-stockholm-convention-environmental-and-analytical-update",bookSignature:"Tomasz Puzyn and Aleksandra Mostrag-Szlichtyng",coverURL:"https://cdn.intechopen.com/books/images_new/872.jpg",editedByType:"Edited by",editors:[{id:"84887",title:"Dr.",name:"Tomasz",surname:"Puzyn",slug:"tomasz-puzyn",fullName:"Tomasz Puzyn"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"52979",title:"Herbivore Adaptations to Plant Cyanide Defenses",doi:"10.5772/66277",slug:"herbivore-adaptations-to-plant-cyanide-defenses",body:'\nHerbivores are a main threat for plants as their feeding destroys vegetative and generative parts of the plant, that is, organs needed for assimilation, nutrient storage and reproduction. In order to cut their losses, plants have developed physical and chemical defenses to fight off herbivores and to survive in their ecosystem. Very effective means to defend against predators are provided by the so-called specialized (or “secondary”) metabolism, which is not required for growth and development, but for the plant’s interaction with its environment [1, 2]. Specialized metabolism is the source of diverse low molecular weight compounds such as alkaloids, terpenes, glucosinolates or cyanogenic glucosides, which are often specific to certain families or species. These compounds may repel the potential predator before contact or harm the herbivore upon ingestion. Defensive metabolites may have herbivore-specific effects or be universally toxic. In the latter case, they need to be stored in an inactive or nontoxic form in the plant to avoid self-intoxication.
\nChemical defense through cyanide is widespread in the plant kingdom. As a universal respiration toxin, cyanide is not accumulated in free form in plants but released from cyanogenic precursors upon tissue damage (“cyanide bomb”), in the course of metabolic reactions in intact plant tissue or upon ingestion by herbivores (Figure 1). The acute and universal toxicity of cyanide in combination with its frequent occurrence in the plant kingdom calls for efficient cyanide detoxification mechanisms in herbivores. As soon as cyanide is liberated upon ingestion of cyanogenic plant material, an enzymatic detoxification is vital for the protection of the herbivore’s cellular metabolism. Although diverse enzymatically catalyzed reactions for the detoxification of cyanide have been described in microorganisms [3], only two main pathways of cyanide detoxification are present in higher animals. These are on the one hand the rhodanese or 3-mercaptopyruvate sulfurtransferase-catalyzed transfer of sulfur from a donor substrate to cyanide, leading to the formation of thiocyanate, and, on the other hand, the β-cyanoalanine synthase-catalyzed substitution of cysteine’s sulfhydryl group by cyanide, leading to the formation of β-cyanoalanine.
Sources of cyanogenesis upon herbivory. Exemplary precursors, intermediates and reactions leading to the liberation of (hydrogen)cyanide from the four main pathways are shown. (A) Cyanogenic glucoside hydrolysis, (B) metabolism of aromatic glucosinolates in the herbivore
An efficient way to minimize the risk of cyanide poisoning is to prevent its formation. Therefore, herbivorous arthropods that colonize plants with high cyanide potential often possess specialized adaptations, which allow them to avoid cyanide release upon ingestion of plant material. This chapter introduces cyanide as a ubiquitous plant-produced compound and summarizes the present understanding of cyanide detoxification pathways and the involved enzymes as well as the current knowledge on cyanide avoidance mechanisms in herbivores with a special focus on arthropods. As certain arthropod species are able to synthesize cyanogenic compounds themselves and/or to sequester cyanogenic compounds from their food plants, we also discuss cyanogenesis in herbivores from an ecological and evolutionary perspective.
The most common storage form of cyanide in plants is cyanogenic glucosides, which are potent antiherbivore defenses with an additional function as nitrogen storage compounds [4–8]. The intact glucosides are water-soluble and nontoxic compounds, but hydrolysis catalyzed by β-glucosidases liberates the cyanohydrins (α-hydroxynitriles), which, spontaneously or under catalysis by α-hydroxynitrilases, release the hydrogen cyanide next to aldehydes or ketones (Figure 1A) [9]. Their broad distribution among more than 2650 plant species from the pteridophytes, gymnosperms and angiosperms [9, 10] may be explained by their biosynthetic origin. Cyanogenic glucosides are biosynthesized through oxidation of common aliphatic and aromatic amino acids by members of the wide-ranging cytochrome P450 family with oximes and cyanohydrins as intermediates and subsequent
Some cyanogenic glucosides have not only been found in plants, but are sequestered and even biosynthesized
A further class of plant secondary compounds carrying a cyanide group is the cyanolipids, a group of lipids possessing a branched five carbon skeleton with a nitrile group [20]. Cyanolipids occur in the seed oil of diverse species of the Sapindaceae [21]. They are cyanohydrin esters, that is, they possess an esterified hydroxyl group in α-position to the nitrile moiety and will form unstable α-hydroxynitriles upon spontaneous or lipase-catalyzed ester hydrolysis (Figure 1D) [22]. As described above, α-hydroxynitriles are a source of cyanide as they readily decompose either spontaneously or enzymatically catalyzed.
\nCyanide may also be liberated upon metabolism of another group of specialized metabolites, the glucosinolates, inside the herbivore by the consecutive action of plant- and herbivore-expressed enzymes. Glucosinolates are amino acid-derived thioglucosides with a sulfated aldoxime core and a variable side chain [23] (Figure 1B). They are part of the glucosinolate-myrosinase system or “mustard oil bomb,” a constitutive defense mechanism common to all families of the Brassicales. The products arising from glucosinolate hydrolysis have manifold effects on herbivores feeding on Brassicales plants, including general deterrence and toxicity, but may also be perceived by specialist herbivores and their parasitoids as host identification cues [24]. The primary defense compounds derived from this system are the isothiocyanates which result from rearrangement of the aglucone formed upon hydrolysis by co-occurring thioglucosidases (myrosinases) when tissue is disrupted [23, 25]. Besides isothiocyanates, other products such as nitriles, epithionitriles and organic thiocyanate can also be formed depending on the structure of the glucosinolate side chain and the presence of additional plant-expressed proteins, the so-called specifier proteins [26–29]. Cyanide release from a glucosinolate-derived nitrile has been demonstrated to occur in larvae of
Apart from the accumulation of cyanogenic precursors as part of specialized metabolism for defense against herbivores, plants from all families generate cyanide as a by-product during the formation of ethylene, a ubiquitous plant hormone. In the last step of ethylene biosynthesis, the oxidation of 1-aminocyclopropane-1-carboxylic acid to ethylene, one mole of cyanide is liberated per mole of ethylene formed (Figure 1C) [39]. Although the steady-state concentration of cyanide from this pathway is normally kept at a low level of 0.2 μM by action of cyanide detoxifying enzymes [40], this demonstrates the ubiquitous occurrence of cyanide in the feed of herbivores.
\nTaken together, cyanide is universally present in plants and herbivores are frequently confronted with this toxin through their diet. Thus, safe handling of cyanide is a necessary prerequisite for herbivory by both specialists feeding exclusively on cyanide-defended plants and generalists with occasional cyanide ingestion. Nevertheless, a varying cyanide content in the host plant seems to influence generalist herbivory more severely than specialist feeding indicating the existence of efficient adaptations to deal with this toxin [41].
Uptake of the small and simple ion cyanide has tremendous effects on the metabolism of all aerobic cells, resulting from its high reactivity and efficient binding to various proteins of cellular respiration and regulation. The main reason for its acute and universal toxicity is the formation of stable complexes between cyanide and the Fe3+-ion of heme a3 of cytochrome c oxidase, one of the electron carriers in the respiratory chain. Cyanide binds to cytochrome c oxidase and acts as a noncompetitive inhibitor of cytochrome c. This stops electron transfer, leading to termination of the respiratory chain and the citric acid cycle due to a shortage of the electron acceptor NAD+ [42]. The resulting lack of ATP is detrimental to the cell. As a consequence, glycolysis, the alternative, but inefficient pathway of ATP generation, is accelerated in combination with lactic acid fermentation for regeneration of NAD+. In humans, metabolic acidosis resulting from high lactic acid levels is responsible for most of the symptoms of cyanide intoxication [43]. Besides the Fe3+ of cytochrome c oxidase cyanide binds metal ions of various metalloenzymes, in particular molybdoenzymes, and forms Schiff base intermediates with pyridoxal phosphate-dependent enzymes causing an efficient inhibition of a wide range of metabolic reactions and regulatory processes in the cell [44].
\nIn vertebrates, cyanide does not only influence cellular metabolism but also diverse physiological processes. By binding to chemoreceptors, cyanide causes vasoconstriction of main arteries which may lead to cardiac shock or pulmonary edema [43, 45]. In addition, cyanide may increase neurotransmitter release by influencing calcium channels in neural cell membranes [46]. Even sublethal doses of cyanide may harm the brain of mammals by altering the membrane lipid peroxidation and the response of antioxidant enzymes [47].
\nSeveral studies performed by Edwin J. Bond in the 1960s on the beetle
Thus, the mode of action of the poison cyanide is complex, and the lethal effects differ between species. Nevertheless, cyanide is one of the most potent toxins and an efficient and universal weapon of plants against herbivore foraging.
Sulfur transferases such as the rhodanese (thiosulfate:cyanidesulfurtransferase, EC 2.8.1.1; see Figure 2A), and its close relative, the 3-mercaptopyruvate sulfurtransferase (EC 2.8.1.2), are enzymes described in plants, fungi, bacteria and a wide range of animals including snails, insects, fish and mammals (see Figure 3) [52–58]. Enzymatic formation of thiocyanate, the so-called rhodanide, was first described in 1933 using vertebrate tissues as discussed by Lewis [59]. Rhodaneses from mammals have been investigated most thoroughly and most insight has been gained from the examination of human and bovine liver rhodaneses [60, 61]. These two enzymes served to uncover the first protein structure of a rhodanese which revealed two similarly folded “rhodanese domains” [62]. In contrast to the highly similar tertiary structure, the two domains differ strongly in their amino acid sequences in agreement with their divergent functions as C-terminal catalytical and N-terminal regulatory domains [62]. At the level of primary structure, rhodaneses from different organisms show little similarity apart from two conserved, 11–13 amino acids long “signature” regions at the N- and C-termini which are also present in distantly related proteins of the rhodanese superfamily such as cdc25 phosphatase and heat shock proteins [63]. This low identity at the amino acid level and the involvement of single rhodanese domains in aberrant proteins make homology-based identification of rhodaneses from further species difficult. To specify the sulfur transferases involved in cyanide detoxification among the members of the diverse superfamily, the tertiary structure has to be taken into account, classifying the true rhodaneses as tandem domain thiosulfate:cyanide sulfurtransferases [63]. This group also comprises the 3-mercaptopyruvate sulfurtransferases. Both types of enzymes have distinct substrate and product spectra, but are yet interconvertible by few amino acid substitutions [64].
Main cyanide detoxification enzymes. Shown are reactions in which cyanide conversion is catalyzed by rhodanese (A—background: bovine liver rhodanese PDB 1RHD) or β-cyanoalanine synthase (B—background: soy bean β-cyanoalanine synthase PDB 3VBE). Additional rhodanese substrates are also shown (A). The
Occurrence of cyanide detoxification enzymes in living organisms. Selected domains, subkingdoms, phyla and classes are shown in a schematic representation of their phylogenetic relationship. Groups in which enzyme activity has been detected are labeled with a gray area (square for rhodanese, circle for β-cyanoalanine synthase). The area is surrounded by black line if sequences of the corresponding enzymes or their genes have been elucidated. Metabolite data also proved β-cyanoalanine synthase activity in Diplopoda, where activity assays have not been performed to our knowledge. Rhodanese seems to be an ubiquitous enzyme, although no sequence data are available from Arthropoda or Mollusca. In contrast, β-cyanoalanine synthase was detected primarily in plants, bacteria and Arthropoda.
Rhodaneses do not only accept thiosulfate as sulfur donor, but all sulfane anions such as organic sulfanes and persulfides [55, 65]. Next to cyanide, the sulfur atom may be accepted by other thiophilic substrates such as the amino acids cysteine and glutathione [65]. The kinetic mechanism of rhodanese was uncovered with its classical substrates cyanide and thiosulfate by Westley and coworkers [60, 66]. In a ping-pong reaction, the sulfane sulfur atom is abstracted from the donor substrate thiosulfate and bound to a cysteine residue in the active site of rhodanese [62]. This is followed by entrance of the acceptor substrate cyanide into the active site and transfer of the sulfur atom [60, 66]. In contrast, the reaction of 3-mercaptopyruvate sulfurtransferase (which can also convert cyanide to thiocyanate [67]) follows a sequential mechanism with formation of a ternary complex composed of the enzyme and both substrates (3-mercaptopyruvate and cyanide) [68, 69].
\nA main function of the rhodaneses in cyanide detoxification is in agreement with their subcellular localization. Rhodanese activity is predominantly detected in the mitochondria, the site of cellular respiration with the cyanide-susceptible cytochrome c oxidase [70, 71]. Nevertheless, for 3-mercaptopyruvate sulfurtransferase and rhodanese of some species, an additional localization in the cytosolic fraction has been described [55, 71, 72]. The cytosolic enzymes may serve to reduce cyanide levels in this compartment whose components (glycolysis intermediates, proteins) may also be affected by cyanide poisoning (see above) [48]. The reaction product of rhodanese-catalyzed cyanide detoxification, thiocyanate, possesses a toxic potential toward mitochondria which could be an additional reason why rhodanese isoforms are also localized in the cytosol in several species.
\nAlthough a major role of rhodaneses in cyanide detoxification seems likely based on the present knowledge, cyanide detoxification might not be their exclusive physiological function. The ubiquitous occurrence of rhodaneses in organisms and tissues with no obvious cyanide exposure as well as the low physiological concentration of their substrate thiosulfate in the mitochondria has fueled doubts about their main role in cyanide detoxification [73]. In support of a major role in cyanide detoxification in mammals, rhodanese activity is inducible in rats by exposition to cyanide or supplementation with thiosulfate [74, 75].
The main enzyme of cyanide detoxification in plants and many bacteria, β-cyanoalanine synthase (EC 4.4.1.9, Figures 2B and 3), belongs to the family of β-substituted alanine synthases sharing the cofactor pyridoxal-5′-phosphate and a uniform fold [80, 81]. This family also comprises
Next to amino acid biosynthesis, β-substituted alanine synthases are involved in cellular sulfur and redox homeostasis [84, 91–93]. Cyanide detoxification by these enzymes is mainly catalyzed by β-cyanoalanine synthases, but
β-Cyanoalanine itself may also exert harmful effects. It has been identified as a neurotoxin and can also be lethal to plants [96, 97]. In order to protect themselves from poisoning with β-cyanoalanine and to minimize costs, plants and microorganisms are able to turn over β-cyanoalanine by nitrile hydratases and nitrilases [98]. Nitrile hydratases catalyze the addition of a water molecule to β-cyanoalanine leading to the formation of the proteinogenic amino acid asparagine. Nitrilases convert β-cyanoalanine to the proteinogenic amino acid aspartate by addition of two water molecules [99]. In addition, the conversion of β-cyanoalanine to asparagine with γ-glutamyl-β-cyanoalanine as an intermediate has been described for some plants [96]. Recycling of β-cyanoalanine has also been shown in some arthropod species (see below). Due to its neurotoxic effect, β-cyanoalanine stored in the defensive droplets of the cyanogenic lepidopteran species
In mammals, rhodanese is generally believed to be the major enzyme for cyanide detoxification, while β-cyanoalanine synthase activity has not been detected in a mammal so far. A comparison of rhodanese activity between mammalian herbi-, omni- and carnivores shows highest activities in herbivores, especially in ruminants which feed on a broad range of plant material including plants with high cyanide potential [58]. In several mammalian species such as plant-feeding rabbits, rhodanese activity is ubiquitously distributed in the body with the highest activity in hepatocytes, the main detoxification site of e.g. xenobiotics [101, 102]. Rhodanese activity is also localized in the mammalian brain, where cyanide acts as a neuromodulator [63].
Intensive research on mammalian rhodaneses also raised the question whether these enzymes are involved in cyanide detoxification in other animals. Rhodanese activity is widely distributed in insects and occurs in snails (see Figure 3) [55, 103]. The level of activity is comparable to that of mammalian gut tissue [53]. However, activity levels are largely in the same range among herbivores which frequently or rarely encounter high cyanide levels. The basal rhodanese activity might be sufficient to capture dietary cyanide in herbivores regardless of the cyanide level in the diet. Alternatively, the uniform distribution of rhodanese activity among herbivores could indicate that arthropod rhodaneses possess an additional function unrelated to cyanide detoxification. This would likely require other mechanisms of cyanide detoxification such as β-cyanoalanine synthase activity [103]. In agreement with this, β-cyanoalanine activity has been found to be broadly distributed in arthropod herbivores (see Figure 3) [86, 95, 104]. In support of the activity data, labeled β-cyanoalanine can be detected in arthropods after feeding of or exposition to isotopically labeled cyanide [30, 105]. Further support for the relevance of β-cyanoalanine synthases comes from experiments with several cyanide-forming lepidopteran species in whose defensive glands β-cyanoalanine and its hydration product asparagine were detected [106]. In millipedes, β-cyanoalanine synthase-catalyzed detoxification of cyanide and further metabolism of β-cyanoalanine to asparagine was demonstrated by studies with radiolabeled precursors [14, 107]. For insects, a similar utilization of cyanide for the formation of proteinogenic amino acids using β-cyanoalanine as an intermediate has been discussed [18], but has only be proven for one beetle by radioactive feeding experiments so far [108]. In the beetle, the radioactive label was recovered from a polypeptide rich in aspartate, the product of nitrilase-catalyzed conversion of β-cyanoalanine [108].
\nIn order to estimate the relevance of rhodanese
Most β-cyanoalanine synthase activity data for animals were generated with intact, partly dried and stored animal tissues, but some enzymes have been purified and characterized [84, 104]. In the nematode
In general, proteins involved in the adaptation of herbivores to their host plants and, in particular, those catalyzing the detoxification and transport of host plant xenobiotics are thought to be under narrow transcriptional regulation [114]. For the mite β-cyanoalanine synthase, an induction by cyanide exposure over 30 generations led to a transcriptional response allowing for the identification of the detoxification enzyme [87]. Thus, these enzymes are among the most variable ones and play a key role in the adaptation to and population of new host plants [114]. As the relationship between herbivore and host plant is close and evolution favors adapted defense of the plant in order to diminish resource and tissue loss through predation [115], transcriptional responses could be discovered also in the host plant [114]. This close coevolution between herbivores and their host plants has therefore shaped both partners and is likely to underlie the higher cyanide tolerance of specialist herbivores on cyanogenic plants [30, 115].
Next to efficient means of cyanide detoxification, herbivores have developed alternative ways to avoid intoxications when feeding on cyanide-defended plants. Often, the cyanide potential of food plants is below a toxic threshold [116]. As generalist herbivores usually change their food plants frequently, this allows them to mix a cyanide-rich diet with a diet low in cyanide to keep the overall cyanide intake below a toxic threshold [116]. Moreover, cyanogenic glucoside occurrence is often accompanied by a bitter taste of the potential food plant and many herbivores therefore avoid feeding on these plants if other host plants are available [116]. Nevertheless, in no-choice feeding experiments or if no other food plant is available in the habitat, herbivores may consume high amounts of cyanide-defended plants leading to intoxication or even death [116, 117]. Adaptations to reduce this risk include morphological, behavioral, physiological and biochemical mechanisms as outlined in the following paragraphs.
\nThe mouthparts of herbivores from the Aphididae have evolved to specialized sucking styli which they insert through the apoplast into the sieve elements to suck phloem sap. This feeding mode avoids tissue disruption and therefore the mixing of plant cyanogenic glucosides and their spatially separated hydrolysis enzymes [41, 116, 118, 119]. In the lepidopteran specialist
As a physiological adaptation, the strongly alkaline midgut pH found in some generalist and specialist herbivores allows for the inhibition of the ingested plant β-glucosidases and avoidance of cyanide liberation [118, 120] in contrast to other species with a slightly acidic midgut pH that are prone to cyanide intoxication [121, 122]. Further, properties and expression of the herbivore’s endogenous β-glucosidases have undergone adaptational adjustments to reduce cyanide release from ingested plant material. As an example, the β-glucosidases localized in the saliva and midgut lumen of the cyanogenic glucoside-feeding specialist
Yet another mechanism protects millipede species (Diplopoda) from cyanide poisoning. These animals possess a highly tolerant cytochrome c oxidase, making cyanide poisoning less effective [125]. Instead of or in combination with a cyanide-resistant terminal oxidase, a complete cyanide-insensitive oxidative pathway has also been proposed [126]. Studies on the respiratory rate of larvae of the lepidopteran generalist herbivore,
Arthropods are the only phylum of animals in which biosynthesis or sequestration of cyanogenic compounds has been shown [15]. Within arthropods, the presence of cyanogenic glucosides appears to be restricted to millipedes (Diplopoda), centipedes (Chilopoda) and three orders within the Insecta (Lepidoptera, Coleoptera and Hemiptera) [128]. The Lepidoptera and Hemiptera are the only groups containing cyanogenic compounds with aliphatic side chains, while in the others groups of arthropods, cyanogenic compounds possess aromatic side chains [4, 129]. Among the most intensely studied species, larvae of
First indications for
Biosynthesis of cyanogenic defense compounds in arthropods. Shown are the most widespread compounds and the enzymes characterized or proposed for the corresponding pathway. The biosynthesis of linamarin and lotaustralin in
Among arthropods, millipedes also contain cyanogenic compounds, namely cyanohydrins such as mandelonitrile, and use them as defense against predators as discussed by Shear [133]. Synthesis of cyanide and cyanohydrins such as mandelonitrile was demonstrated for different species of millipedes using feeding tests with 14C-phenylalanine and further radioactively labeled precursors [14, 107, 138]. As this resulted in labeling of phenylacetaldoxime and phenylacetonitrile as potential pathway intermediates, a biosynthesis pathway very alike the one described in plants and later in insects was proposed [14, 107, 138] (Figure 4). The unwanted release of cyanide is prevented by specifically shaped, two chamber glands where cyanide precursor and the hydrolyzing enzyme α-hydroxynitrile lyase are stored separately [107, 133]. In the α-hydroxynitrile chamber, organic acids generate low pH values to stabilize the α-hydroxynitrile [133]. Upon attack by a predator, gland secretions are mixed to generate cyanide. This mechanism allows the millipede to liberate cyanide in a controlled way, thereby economizing its chemical defense and protecting its own tissue from poisoning.
\nAlthough the presence of cyanogenic glucosides and, in part, their
Most data known on sequestration of cyanogenic compounds in insects were generated using larvae of
Sequestration of cyanogens has also been shown for gynocardin, a cyclic α-hydroxynitrile glucoside, in
Larvae of the bug
Cyanogenic glucosides derived from
Nevertheless, cyanide alone is not always efficient for the animal’s defense. It has been shown that in millipedes, not cyanide itself but the second product of mandelonitrile hydrolysis, benzaldehyde, is repellent to ants [49]. In contrast, for the intact cyanogenic glucoside cardiospermin a deterrent effect on ants has been shown which could not be observed for any cyanogenic glucoside before [129]. Thus, predating insects facing cyanide in their prey may have evolved a sensitive perception of substances with stronger odor or taste usually occurring alongside cyanide [49]. Alternatively, it was proposed that cyanide is the main means of defense against vertebrate predators, while benzaldehyde is used to repel arthropod enemies [133]. Phylogenetic and physiological data indicate that cyanogenesis as defense strategy has been lost and replaced by ancient phenolic defense compounds in some groups among the Polydesmida, mainly those unlikely to be targeted by vertebrate predators [133].
\nNext to their defensive roles, linamarin and lotaustralin are also used as nitrogen sources for chitin biosynthesis based on their turnover during metamorphosis [146]. During the formation of the pupal cuticle, cyanogenic glucosides are a key nitrogen source [146, 147]. However, mobilization through β-cyanoalanine synthase and nitrilase/nitrile hydratase leading to the formation of asparagine and aspartate similar to plants [148] has not been demonstrated in insects so far. The efficient transport of cyanogenic glucosides in
Based on transcriptional and metabolite analyses [149], it has been hypothesized that the biosynthesis of cyanogenic glucosides in arthropods is older than their sequestration [149]. The biosynthesis is thought to have been constitutive in the ancestors of Zygaena which did not live on cyanogenic plants (but on Celastraceae) and were, therefore, not able to receive cyanogenic glucosides from their host plants. Upon exploration of cyanogenic plants, the insects’ endogenous biosynthesis became inducible as sequestration helped to reduce metabolic costs for
The past 15 years have witnessed an enormous progress in our understanding of herbivore adaptational mechanisms to plant cyanide defenses and their evolution. A lot of the present knowledge has been acquired through the application of state-of-the-art analytical and molecular tools as well as imaging techniques to the model species
Future research will have to extend the present insights by studying a broader range of species with respect to their behavioral, physiological and biochemical adaptations to cyanogens. Besides the identification and detailed characterization of cyanide detoxification enzymes from additional species, transporters involved in cyanogen sequestration will be an interesting target of future investigations. In addition, experimental proof of essential roles of herbivore proteins involved in overcoming plant cyanide defenses might become possible
Financial support of our research on cyanide detoxification in arthropods by the German Research Foundation is gratefully acknowledged.
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.
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].
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.
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
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.
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].
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].
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.
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,
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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