IntechOpen was founded by scientists, for scientists, in order to make book publishing accessible around the globe. Over the last two decades, this has driven Open Access (OA) book publishing whilst levelling the playing field for global academics. Through our innovative publishing model and the support of the research community, we have now published over 5,700 Open Access books and are visited online by over three million academics every month. These researchers are increasingly working in broad technology-based subjects, driving multidisciplinary academic endeavours into human health, environment, and technology.
\\n\\n
By listening to our community, and in order to serve these rapidly growing areas which lie at the core of IntechOpen's expertise, we are launching a portfolio of Open Science journals:
All three journals will publish under an Open Access model and embrace Open Science policies to help support the changing needs of academics in these fast-moving research areas. There will be direct links to preprint servers and data repositories, allowing full reproducibility and rapid dissemination of published papers to help accelerate the pace of research. Each journal has renowned Editors in Chief who will work alongside a global Editorial Board, delivering robust single-blind peer review. Supported by our internal editorial teams, this will ensure our authors will receive a quick, user-friendly, and personalised publishing experience.
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"By launching our journals portfolio we are introducing new, dedicated homes for interdisciplinary technology-focused researchers to publish their work, whilst embracing Open Science and creating a unique global home for academics to disseminate their work. We are taking a leap toward Open Science continuing and expanding our fundamental commitment to openly sharing scientific research across the world, making it available for the benefit of all." Dr. Sara Uhac, IntechOpen CEO
\\n\\n
"Our aim is to promote and create better science for a better world by increasing access to information and the latest scientific developments to all scientists, innovators, entrepreneurs and students and give them the opportunity to learn, observe and contribute to knowledge creation. Open Science promotes a swifter path from research to innovation to produce new products and services." Alex Lazinica, IntechOpen founder
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In conclusion, Natalia Reinic Babic, Head of Journal Publishing and Open Science at IntechOpen adds:
\\n\\n
“On behalf of the journal team I’d like to thank all our Editors in Chief, Editorial Boards, internal supporting teams, and our scientific community for their continuous support in making this portfolio a reality - we couldn’t have done it without you! With your support in place, we are confident these journals will become as impactful and successful as our book publishing program and bring us closer to a more open (science) future.”
\\n\\n
We invite you to visit the journals homepage and learn more about the journal’s Editorial Boards, scope and vision as all three journals are now open for submissions.
\\n\\n
Feel free to share this news on social media and help us mark this memorable moment!
After years of being acknowledged as the world's leading publisher of Open Access books, today, we are proud to announce we’ve successfully launched a portfolio of Open Science journals covering rapidly expanding areas of interdisciplinary research.
\n\n\n\n
IntechOpen was founded by scientists, for scientists, in order to make book publishing accessible around the globe. Over the last two decades, this has driven Open Access (OA) book publishing whilst levelling the playing field for global academics. Through our innovative publishing model and the support of the research community, we have now published over 5,700 Open Access books and are visited online by over three million academics every month. These researchers are increasingly working in broad technology-based subjects, driving multidisciplinary academic endeavours into human health, environment, and technology.
\n\n
By listening to our community, and in order to serve these rapidly growing areas which lie at the core of IntechOpen's expertise, we are launching a portfolio of Open Science journals:
All three journals will publish under an Open Access model and embrace Open Science policies to help support the changing needs of academics in these fast-moving research areas. There will be direct links to preprint servers and data repositories, allowing full reproducibility and rapid dissemination of published papers to help accelerate the pace of research. Each journal has renowned Editors in Chief who will work alongside a global Editorial Board, delivering robust single-blind peer review. Supported by our internal editorial teams, this will ensure our authors will receive a quick, user-friendly, and personalised publishing experience.
\n\n
"By launching our journals portfolio we are introducing new, dedicated homes for interdisciplinary technology-focused researchers to publish their work, whilst embracing Open Science and creating a unique global home for academics to disseminate their work. We are taking a leap toward Open Science continuing and expanding our fundamental commitment to openly sharing scientific research across the world, making it available for the benefit of all." Dr. Sara Uhac, IntechOpen CEO
\n\n
"Our aim is to promote and create better science for a better world by increasing access to information and the latest scientific developments to all scientists, innovators, entrepreneurs and students and give them the opportunity to learn, observe and contribute to knowledge creation. Open Science promotes a swifter path from research to innovation to produce new products and services." Alex Lazinica, IntechOpen founder
\n\n
In conclusion, Natalia Reinic Babic, Head of Journal Publishing and Open Science at IntechOpen adds:
\n\n
“On behalf of the journal team I’d like to thank all our Editors in Chief, Editorial Boards, internal supporting teams, and our scientific community for their continuous support in making this portfolio a reality - we couldn’t have done it without you! With your support in place, we are confident these journals will become as impactful and successful as our book publishing program and bring us closer to a more open (science) future.”
\n\n
We invite you to visit the journals homepage and learn more about the journal’s Editorial Boards, scope and vision as all three journals are now open for submissions.
\n\n
Feel free to share this news on social media and help us mark this memorable moment!
\n\n
\n'}],latestNews:[{slug:"webinar-introduction-to-open-science-wednesday-18-may-1-pm-cest-20220518",title:"Webinar: Introduction to Open Science | Wednesday 18 May, 1 PM CEST"},{slug:"step-in-the-right-direction-intechopen-launches-a-portfolio-of-open-science-journals-20220414",title:"Step in the Right Direction: IntechOpen Launches a Portfolio of Open Science Journals"},{slug:"let-s-meet-at-london-book-fair-5-7-april-2022-olympia-london-20220321",title:"Let’s meet at London Book Fair, 5-7 April 2022, Olympia London"},{slug:"50-books-published-as-part-of-intechopen-and-knowledge-unlatched-ku-collaboration-20220316",title:"50 Books published as part of IntechOpen and Knowledge Unlatched (KU) Collaboration"},{slug:"intechopen-joins-the-united-nations-sustainable-development-goals-publishers-compact-20221702",title:"IntechOpen joins the United Nations Sustainable Development Goals Publishers Compact"},{slug:"intechopen-signs-exclusive-representation-agreement-with-lsr-libros-servicios-y-representaciones-s-a-de-c-v-20211123",title:"IntechOpen Signs Exclusive Representation Agreement with LSR Libros Servicios y Representaciones S.A. de C.V"},{slug:"intechopen-expands-partnership-with-research4life-20211110",title:"IntechOpen Expands Partnership with Research4Life"},{slug:"introducing-intechopen-book-series-a-new-publishing-format-for-oa-books-20210915",title:"Introducing IntechOpen Book Series - A New Publishing Format for OA Books"}]},book:{item:{type:"book",id:"9076",leadTitle:null,fullTitle:"Recent Advances in Wound Healing",title:"Recent Advances in Wound Healing",subtitle:null,reviewType:"peer-reviewed",abstract:"The human wound-healing process could be divided into four discrete phases, which have also been indicated as the hemostasis, the inflammatory, the proliferation, and the remodeling phase. For a wound to be healed efficaciously, all four phases must sequentially happen at an expected time setting. Numerous aspects can hinder one or more stages of this procedure, thus can cause inappropriate or diminished wound healing. This book reviews the recent literature on the most significant factors that affect wound healing and the potential cellular and/or molecular mechanisms involved. The factors discussed include physiology of wound healing, interferon, stem cells and photobiomodulation, chronic venous ulcer, chronic fistula, bionanomaterials, topical antiseptic agents, including silver and sodium hypochlorite solution, diabetic ulcers, and nutritional supplements such as copper.",isbn:"978-1-83968-573-6",printIsbn:"978-1-83968-572-9",pdfIsbn:"978-1-83968-574-3",doi:"10.5772/intechopen.83072",price:119,priceEur:129,priceUsd:155,slug:"recent-advances-in-wound-healing",numberOfPages:214,isOpenForSubmission:!1,isInWos:null,isInBkci:!1,hash:"5e10a897612bf74c88669ab634de6459",bookSignature:"Shahin Aghaei",publishedDate:"March 2nd 2022",coverURL:"https://cdn.intechopen.com/books/images_new/9076.jpg",numberOfDownloads:1977,numberOfWosCitations:0,numberOfCrossrefCitations:2,numberOfCrossrefCitationsByBook:0,numberOfDimensionsCitations:3,numberOfDimensionsCitationsByBook:0,hasAltmetrics:0,numberOfTotalCitations:5,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"August 26th 2020",dateEndSecondStepPublish:"November 30th 2020",dateEndThirdStepPublish:"January 29th 2021",dateEndFourthStepPublish:"April 19th 2021",dateEndFifthStepPublish:"June 18th 2021",currentStepOfPublishingProcess:5,indexedIn:"1,2,3,4,5,6",editedByType:"Edited by",kuFlag:!1,featuredMarkup:null,editors:[{id:"64024",title:"Associate Prof.",name:"Shahin",middleName:null,surname:"Aghaei",slug:"shahin-aghaei",fullName:"Shahin Aghaei",profilePictureURL:"https://mts.intechopen.com/storage/users/64024/images/system/64024.jpg",biography:"Shahin Aghaei, MD, graduated from Shiraz University of Medical Sciences, Shiraz, Iran, in 2004. He was awarded a fellowship from the International Society of Dermatopathology (ISD) from Charles University in Prague, the Czech Republic, in 2008 and a fellowship of Dermatologic Surgery from the Medical University of Graz, Austria, in 2010. He is currently editor in chief of the Journal of Surgical Dermatology in Singapore and associate professor of Dermatology and Dermatologic Surgery at Iran University of Medical Sciences School of Medicine, Tehran, Iran. He is also a member of the following medical societies: American Academy of Dermatology, European Academy of Dermatology and Venereology, American Society for Laser Medicine and Surgery, International Society of Dermatology, International Hyperhidrosis Society, and Iranian Society of Dermatology.",institutionString:"Iran University of Medical Sciences",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"2",institution:{name:"Iran University of Medical Sciences",institutionURL:null,country:{name:"Iran"}}}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"193",title:"Pathology",slug:"medicine-pathology"}],chapters:[{id:"75901",title:"Interferon Therapy for Hypertrophic Scars and Keloids",doi:"10.5772/intechopen.96789",slug:"interferon-therapy-for-hypertrophic-scars-and-keloids",totalDownloads:242,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:"Interferons (IFNs) belong to the family of cytokines are widely used to treat keloids owing to their ability to increase collagenase activity thereby reducing the production of collagen and other extracellular matrix (ECM). Intralesional injection of IFN-α – 2b increases the collagenase level by inhibiting the secretion of metalloproteinases, an inhibitor of collagenase. Moreover, the anti-fibrotic activity of IFNs, interfere with fibroblast mediated collagen synthesis. On the other hand, combinatorial therapy has been preferred recently along with IFN due to its side effects observed in various clinical trials conducted only with IFN. Triamcinolone acetonide (TAC) and CO2 lasers along with IFNs are found to be the potential therapy for the treatment of scars and keloids. In this chapter, IFN mediated therapy for the treatment of scars and keloids, its benefits and limitations and the advantages of combinatorial therapy with the appropriate literature support are discussed.",signatures:"Amalorpava Mary Loordhuswamy and Santhini Elango",downloadPdfUrl:"/chapter/pdf-download/75901",previewPdfUrl:"/chapter/pdf-preview/75901",authors:[{id:"332100",title:"Dr.",name:"Santhini",surname:"Elango",slug:"santhini-elango",fullName:"Santhini Elango"},{id:"332102",title:"Dr.",name:"Amalorpava Mary",surname:"Loordhuswamy",slug:"amalorpava-mary-loordhuswamy",fullName:"Amalorpava Mary Loordhuswamy"}],corrections:null},{id:"75914",title:"The Need for Basic, Translational, and Clinical Research in the Field of Hypertrophic Scars",doi:"10.5772/intechopen.96943",slug:"the-need-for-basic-translational-and-clinical-research-in-the-field-of-hypertrophic-scars",totalDownloads:126,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:"Hypertrophic scar (HTS) is a fibrotic skin disorder that is marked by excessive inflammation and extracellular matrix deposition in response to cutaneous traumatic injuries such as burns, lacerations, incisions, and abrasions. HTS has various risk factors, available treatments, and treatment effectiveness. Research at the basic, translational, and clinical levels are in their infancy compared to fibrotic diseases in other organ systems. This chapter will review current in vitro and in vivo modeling, and highlight research needs to address gaps in the study of HTS. The following topics will be discussed in the chapter: a. Basic Science Research i. Seminal findings ii. Limitations to these models iii. Suggestions for topics of future research b. Translational Science Research i. Seminal findings ii. Limitations to these models iii. Suggestions for topics of future research c. Clinical Research i. Seminal findings ii. Limitations to these models iii. Suggestions for topics of future research.",signatures:"Bonnie C. Carney, Jeffrey W. Shupp and Taryn E. Travis",downloadPdfUrl:"/chapter/pdf-download/75914",previewPdfUrl:"/chapter/pdf-preview/75914",authors:[{id:"182585",title:"Dr.",name:"Jeffrey W.",surname:"Shupp",slug:"jeffrey-w.-shupp",fullName:"Jeffrey W. Shupp"},{id:"297718",title:"BSc.",name:"Bonnie C.",surname:"Carney",slug:"bonnie-c.-carney",fullName:"Bonnie C. Carney"},{id:"332297",title:"Dr.",name:"Taryn E.",surname:"Travis",slug:"taryn-e.-travis",fullName:"Taryn E. Travis"}],corrections:null},{id:"76812",title:"Pharyngocutaneous Fistulas Following Total Laryngectomy",doi:"10.5772/intechopen.97848",slug:"pharyngocutaneous-fistulas-following-total-laryngectomy",totalDownloads:250,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:"Total laryngectomy is still the final therapeutic solution in cases of locally advanced laryngeal cancer, as well as in cases of therapeutic failure of organ-sparing surgery or radiation therapy. Following excision of the larynx, the remaining pharynx is reconstructed to obtain continuity of the upper digestive tract. One of the most common complications in these patients, despite constant refinement of the procedure, is the development of a pharyngo-cutaneous fistula. These fistulas prolong hospital stay and often require a second surgical procedure, increasing morbidity and cost for the patient, while diminishing his quality of life. Some risk-factors have been identified, but only some may be corrected before surgery to lower this risk. Managing the fistula once present depends on multiple factors, essential being the size of the fistula as well as the position and concomitant factors, with options ranging from conservative measures to aggressive reconstructive surgery with local miocutaneous flaps. Modern vocal rehabilitation with T.E.P. (tracheo-esophageal puncture) and vocal prosthesis placement presents a new challenge – because of the risk of developing a tracheo-esophageal fistula, with an even higher risk for the patient because of tracheal aspiration. Understanding healing mechanisms of these structures is key to proper management of this complication.",signatures:"Alexandru Nicolaescu, Șerban V.G. Berteșteanu, Raluca Grigore, Mihnea Cojocărița-Condeescu, Bogdan Popescu, Catrinel Simion-Antonie, Paula Bejenaru and Simona Gloria Munteanu",downloadPdfUrl:"/chapter/pdf-download/76812",previewPdfUrl:"/chapter/pdf-preview/76812",authors:[{id:"216552",title:"Dr.",name:"Șerban V.G.",surname:"Berteșteanu",slug:"serban-v.g.-bertesteanu",fullName:"Șerban V.G. Berteșteanu"},{id:"216556",title:"Dr.",name:"Alexandru",surname:"Nicolaescu",slug:"alexandru-nicolaescu",fullName:"Alexandru Nicolaescu"},{id:"216562",title:"Dr.",name:"Raluca",surname:"Grigore",slug:"raluca-grigore",fullName:"Raluca Grigore"},{id:"222738",title:"Dr.",name:"Popescu",surname:"Bogdan",slug:"popescu-bogdan",fullName:"Popescu Bogdan"},{id:"317106",title:"Dr.",name:"Mihnea",surname:"Cojocarita-Condeescu",slug:"mihnea-cojocarita-condeescu",fullName:"Mihnea Cojocarita-Condeescu"},{id:"350508",title:"Dr.",name:"Catrinel",surname:"Simion-Antonie",slug:"catrinel-simion-antonie",fullName:"Catrinel Simion-Antonie"},{id:"350509",title:"Dr.",name:"Paula",surname:"Bejenaru",slug:"paula-bejenaru",fullName:"Paula Bejenaru"},{id:"350510",title:"Mrs.",name:"Gloria",surname:"Munteanu",slug:"gloria-munteanu",fullName:"Gloria Munteanu"}],corrections:null},{id:"75765",title:"Combined Administration of Stem Cells and Photobiomodulation on Wound Healing in Diabetes",doi:"10.5772/intechopen.96905",slug:"combined-administration-of-stem-cells-and-photobiomodulation-on-wound-healing-in-diabetes",totalDownloads:183,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:"Wound healing is an active and compound biological course which can be divided into four steps: hemostasis, inflammation, proliferation, and remodeling. Diabetes mellitus induces weakened wound healing by disturbing one or more of the biological functions of these steps. Diabetic foot ulcers result from the simultaneous action of multiple disturbing causes. Mesenchymal stem cells, especially autologous ones, are easily accessible with noninvasive methods and have been shown to provide a regenerative microenvironment at wound sites. Despite current knowledge, major hurdles remain to be overcome in order to achieve effective therapeutic effects. Photobiomodulation is the use of light to reduce pain and inflammation and stimulate healing and the proliferation of stem cells, which would be very useful in increasing stem cell function and in regenerative medicine. The current study analyzes the results of studies using separate and combined administrations of stem cells and photobiomodulation on diabetic wound healing in patients and animal models. We hypothesize that the combined application of photobiomodulation and stem cells will accelerate the repair process and assist the healing of foot ulcers in diabetes mellitus patients.",signatures:"Mohammad Bayat and Sufan Chien",downloadPdfUrl:"/chapter/pdf-download/75765",previewPdfUrl:"/chapter/pdf-preview/75765",authors:[{id:"184084",title:"Prof.",name:"Mohammad",surname:"Bayat",slug:"mohammad-bayat",fullName:"Mohammad Bayat"},{id:"256112",title:"Prof.",name:"Sufan",surname:"Chien",slug:"sufan-chien",fullName:"Sufan Chien"}],corrections:null},{id:"76688",title:"Chronic Venous Ulcer",doi:"10.5772/intechopen.97709",slug:"chronic-venous-ulcer",totalDownloads:172,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:1,abstract:"This chapter sheds light on the cause and effect of chronic venous ulcers (CVUs) and the therapeutic procedures used to treat them. In the last two decades, many changes have occurred in the strategy of wound management through the development of adjunctive therapy that supports wound healing. Eventually, the latest development in platelet concentration technology produced platelet-rich fibrin (PRF). It was categorized as the second-generation platelet concentration family after platelet-rich plasma (PRP). Venous leg ulcers (VLUs) account for 70% of all leg ulcers and are estimated to affect 1% of the population; prevalence increases with age. The chronicity and refractory nature of venous ulcers have a great effect on the quality of life (QoL) and work productivity of patients, in addition to the expenditure of significant medical resources and efforts. Therefore, the goal of VLU management is to induce rapid healing without recurrence, which mainly helps to improve QoL. The first therapeutic procedure used in the treatment of VLU was compression therapy, in which the application of effective graduated compression decreased the overload in the venous system and venous reflux. Furthermore, it accelerated the capillary blood flow and decreased capillary fluid leakage, which alleviated limb edema.",signatures:"Walid A.M. Ganod",downloadPdfUrl:"/chapter/pdf-download/76688",previewPdfUrl:"/chapter/pdf-preview/76688",authors:[{id:"311824",title:"M.Sc.",name:"Walid A.M.",surname:"Ganod",slug:"walid-a.m.-ganod",fullName:"Walid A.M. Ganod"}],corrections:[{id:"81442",title:"Corrigendum to: Chronic Venous Ulcer",doi:null,slug:"corrigendum-to-chronic-venous-ulcer",totalDownloads:null,totalCrossrefCites:null,correctionPdfUrl:null}]},{id:"77212",title:"Polymeric Biomaterials for Wound Healing Incorporating Plant Extracts and Extracellular Matrix Components",doi:"10.5772/intechopen.98556",slug:"polymeric-biomaterials-for-wound-healing-incorporating-plant-extracts-and-extracellular-matrix-compo",totalDownloads:181,totalCrossrefCites:0,totalDimensionsCites:1,hasAltmetrics:0,abstract:"Biomaterials are constructed to promote or stimulate the processes of wound healing. Polymeric biomaterials can be used to hydrate the wound and serve as barrier to pathogens with plant extracts, antimicrobial agents and extracellular components incorporated to stimulate the healing process. The biological and physical augmentation provided by extracellular matrix derived implants continues facilitate innovation in biomaterials utilized in management of nonhealing wounds. Tissue-processing methodologies can birth extracellular matrix-based devices with characteristic post-implantation responses ranging from the classic foreign body encapsulation of a permanent implant, to one where the implant is degraded and resorbed, to one where the processed extracellular matrix implant is populated by local fibroblasts and supporting vasculature to produce, a viable and metabolically active tissue. Extracellular matrix components and plant extracts have been shown to possesses pharmacological properties with potential for use in the treatment of skin diseases and wound healing. Antioxidant, anti-inflammatory assays, and wound healing assays have been shown to support the dermatological and wound healing usage of these medicinal plants extracts.",signatures:"Margaret O. Ilomuanya, Ibilola M. Cardoso-Daodu, Uloma N. Ubani-Ukoma and Adannaya C. Adebona",downloadPdfUrl:"/chapter/pdf-download/77212",previewPdfUrl:"/chapter/pdf-preview/77212",authors:[{id:"323005",title:"Dr.",name:"Margaret O.",surname:"Ilomuanya",slug:"margaret-o.-ilomuanya",fullName:"Margaret O. Ilomuanya"},{id:"340258",title:"MSc.",name:"Uloma N.",surname:"Ubani-Ukoma",slug:"uloma-n.-ubani-ukoma",fullName:"Uloma N. Ubani-Ukoma"},{id:"340259",title:"MSc.",name:"Adannaya C.",surname:"Adebona",slug:"adannaya-c.-adebona",fullName:"Adannaya C. Adebona"},{id:"340261",title:"MSc.",name:"Ibilola M.",surname:"Cardoso-Daodu",slug:"ibilola-m.-cardoso-daodu",fullName:"Ibilola M. Cardoso-Daodu"}],corrections:null},{id:"76237",title:"Bionanomaterials: Advancements in Wound Healing and Tissue Regeneration",doi:"10.5772/intechopen.97298",slug:"bionanomaterials-advancements-in-wound-healing-and-tissue-regeneration",totalDownloads:112,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:"Abnormal wound healing represents a major healthcare issue owing to upsurge number of trauma and morbid physiology which ultimately posed a healthcare burden on patient, society and health care organization. A wound healing is a complex process so effective management of chronic wounds is often hard. Recently in addition to many conventional wound treatment’s advances in bionanomaterial are attaining much attention in wound care and skin tissue engineering. Bionanomaterials are biomolecule-based nanocomposite synthesized by plants, microbes and animals which possess high degree of biocompatibility, biodegradability, non-toxicity and bioactive assets. Bioactive assets like antimicrobial, immune modulatory, cell proliferation and angiogenesis of biomolecules forms fortunate microenvironment for the wound healing process. Nature has provided us with a significant set of biomolecules like chitosan, hyaluronic acid, collagen, cellulose, silk fucoidan etc. have been exploited to construct engineered bionanomaterials. These biopolymeric nanomaterials are currently researched comprehensively as they have higher surface to volume ratio and high chemical affinity showing a promising augmentation of deadly wounds. In this chapter we aimed to highlight the biological sources and bioengineering approaches adapted for biopolymers so they facilitate wound healing process.",signatures:"Priyanka Chhabra and Kajol Bhati",downloadPdfUrl:"/chapter/pdf-download/76237",previewPdfUrl:"/chapter/pdf-preview/76237",authors:[{id:"320705",title:"Dr.",name:"Priyanka",surname:"Chhabra",slug:"priyanka-chhabra",fullName:"Priyanka Chhabra"},{id:"329488",title:"MSc.",name:"Kajol",surname:"Bhati",slug:"kajol-bhati",fullName:"Kajol Bhati"}],corrections:null},{id:"79493",title:"Current Understanding to Accelerate Wound Healing: Mechanism and Clinical Importance",doi:"10.5772/intechopen.101429",slug:"current-understanding-to-accelerate-wound-healing-mechanism-and-clinical-importance",totalDownloads:115,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:"Wound mending is a complex organic cycle that brings about the reclamation of tissue honesty. Physiologically, it very well may be separated into four particular periods of hemostasis, inflammation, proliferation, and tissue remodeling (redesigning). This chapter portrays the cellular premise of wound mending and extracellular flagging cycles, which is responsible to control them. The capacity of fibroblasts, neutrophils, platelets, and macrophages is contemplated exhaustively. The idea of mending by essential and optional expectation is talked about. Numerous components are known to unfavorably influence mending including undernourishment, hypoxia, immunosuppression, ongoing sickness, and medical procedure. It is fundamental that specialists comprehend the key physiological cycles associated with mending to limit patient illness from postponed recuperating.",signatures:"Sunil Kumar, Shravan Kumar Paswan, Pritt Verma, Akanksha, RamKishor Sah, Sajal Srivastava and Chandana Venketswara Rao",downloadPdfUrl:"/chapter/pdf-download/79493",previewPdfUrl:"/chapter/pdf-preview/79493",authors:[{id:"89143",title:"Dr.",name:"Chandana Venketeswara",surname:"Rao",slug:"chandana-venketeswara-rao",fullName:"Chandana Venketeswara Rao"},{id:"299436",title:"Mr.",name:"Sunil",surname:"Kumar",slug:"sunil-kumar",fullName:"Sunil Kumar"},{id:"302657",title:"Dr.",name:"Sajal",surname:"Srivastava",slug:"sajal-srivastava",fullName:"Sajal Srivastava"},{id:"342214",title:"Ph.D.",name:"Shravan Kumar",surname:"Paswan",slug:"shravan-kumar-paswan",fullName:"Shravan Kumar Paswan"},{id:"428874",title:"Dr.",name:"Pritt",surname:"Verma",slug:"pritt-verma",fullName:"Pritt Verma"},{id:"428875",title:"Ms.",name:"Akanksha",surname:null,slug:"akanksha",fullName:"Akanksha null"}],corrections:null},{id:"75798",title:"Copper, an Abandoned Player Returning to the Wound Healing Battle",doi:"10.5772/intechopen.96952",slug:"copper-an-abandoned-player-returning-to-the-wound-healing-battle",totalDownloads:353,totalCrossrefCites:2,totalDimensionsCites:2,hasAltmetrics:0,abstract:"Copper has two key properties that endow it as an excellent active ingredient to be used in the “wound healing battle”. First, copper plays a key role in angiogenesis, dermal fibroblasts proliferation, upregulation of collagen and elastin fibers production by dermal fibroblasts, and it serves as a cofactor of Lysyl oxidase needed for efficient dermal extracellular matrix (ECM) protein cross-linking. Secondly, copper has potent wide-spectrum biocidal properties. Both gram-positive and gram-negative bacteria, including antibiotic resistant bacteria and hard to kill bacterial spores, fungi and viruses, when exposed to high copper concentrations, are killed. Copper has been used as a biocide for centuries by many different civilizations. Impregnation of copper oxide microparticles in wound dressings allows continuous release of copper ions. This results not only in the protection of the wounds and wound dressings from pathogens, but more importantly, enhances wound healing. The article discusses the molecular mechanisms of enhanced wound healing by the copper oxide impregnated dressings, which include in situ upregulation of pro-angiogenic factors and increased blood vessel formation. It also includes clinical cases showing clearance of infection, induction of granulation and epithelialization of necrotic wounds, reduction of post-operative swelling inflammation and reduction of scar formation, in wounds when they were treated with copper oxide impregnated dressings. We show the positive outcome at all wound healing stages of using the copper impregnated wound dressings, indicating the neglected critical role copper plays in wound healing.",signatures:"Gadi Borkow and Eyal Melamed",downloadPdfUrl:"/chapter/pdf-download/75798",previewPdfUrl:"/chapter/pdf-preview/75798",authors:[{id:"341173",title:"Ph.D.",name:"Gadi",surname:"Borkow",slug:"gadi-borkow",fullName:"Gadi Borkow"}],corrections:null},{id:"76461",title:"Contribution of Topical Agents to Wound Healing",doi:"10.5772/intechopen.97170",slug:"contribution-of-topical-agents-to-wound-healing",totalDownloads:243,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:"The process of wound healing is often accompanied by bacterial infection or critical colonization, which leads to an extension of the inflammatory response phase and delayed epithelization. In the review of scientific articles, we found the description and mode of action of topical antiseptic agents, including silver and sodium hypochlorite solution, to control the spread of microorganisms. The value of hyaluronic acid for wound healing is described. Furthermore, a novel treatment option with microspheres is mentioned. 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1. Introduction
Since the first discovery of amorphous alloys in the twentieth century, by Kramer [1] in the 1930s through vapor deposition, succeeded by Brenner et al. [2] in the 1950s through electrodeposition, and then by Klement et al. [3] in the 1960s through rapidly quenching casting processes (related to Au70Si30 glassy alloy system), several bulk glass-forming systems have emerged. Further innovation in this novel area of materials science has accredited a potential market for commercial applications of metallic glasses. As a result, increased research on various tribological and corrosion properties of BMGs has occurred. The first published information on the corrosion properties of metallic glasses appeared in 1974 (it concerned the Fe-Cr-P-C alloy system) [4]. Since then, the corrosion behavior of all classes of metallic glasses and/or amorphous nanocrystalline alloys has been of great concern.
2. Corrosion resistance of bulk metallic glasses
The corrosion resistance is a critical factor for considering bulk metallic glasses (BMGs) used in hostile or chemical environments. However, there has been a growing interest in the corrosion behavior of these amorphous alloys.
At first presumption, many metallic glasses exhibit extremely good corrosion resistance, but there is a controversy over the exact mechanism(s) responsible for such improvement with respect to their crystalline counterparts. There are several possibilities for explaining the difference in corrosion behavior between amorphous and crystalline metals. The good corrosion resistance of single-phase glasses is often attributed to structure, composition, as well as structural and compositional homogeneity. Both the chemical homogeneity and the absence of microstructure in these amorphous alloys are most likely source of their superiority over their crystalline candidates. It has commonly been assumed that the very short solid-state diffusion time caused by the rapid cooling rates (as high as 106 K s−1) required to produce the amorphous alloys, prevents the chemical heterogeneity and crystallization (but not always) [5].
When diffusion in the solid-state is kept faster and faster enough, the yielded homogeneous amorphous alloys should lack grain boundaries, dislocations, second-phase particles, segregates and other structural defects. These structural impurities are often present and commonly the culprits behind the localized corrosion (e.g., pitting, galvanic corrosion, etc.) observed in their crystalline counterpart alloys exposed to an aggressive environment. Corrosion readily occurs preferentially at such defect sites; therefore, metallic glasses can be expected to exhibit better corrosion resistance than crystalline alloys. Nevertheless, it has been shown that this statement does not always apply to BMGs [6]. Indeed, second phases (crystalline inclusions) were observed in some BMGs even after treatment. This was attributed to heterogeneous nucleation reactions caused by impurities in the melt that remained on the metal surface of the finished good [7].
Under normal working conditions, cathodes and anodes, possibly small but sufficiently large to cause localized corrosion, can be formed on the same metal glassy surface. Corrosion at the origin of these local crystalline inclusions will be greatly amplified upon conditions and can cause corrosion pits. This is one of the reasons why the persistent quest for BMG systems with increased glass-forming ability (i.e., decreased crystalline inclusions, see previous chapter) has provided the field with an influx of new alloying BMGs and compositions.
The ability of metals for alloying has provided the key to achieve enhanced properties, but certain elements are more common than others are. It is mainly the combined effect of the alloying elements, the test environment and, to some extent, earlier specific treatment conditions, which determines the electrochemical properties profile of a number of metallic glasses. The addition of simple metals (SM), transition metals (early and late TM), and rare earth metals (REM) to the base metal was, inter alia, the principal strategy used to produce a selection of different metallic material glasses with a broad range of alloy compositions. According to IUPAC definition, a transition metal (TM) is defined as “a chemical element whose atoms have an incomplete d electronic sub-shell, or which can form cations whose electronic sub-shell d is incomplete.”
The early versus late transition metals differ generally in their oxidation states (each metal has different possible oxidation states). Electrons have a stronger attraction to the protons in the late transition metals (LTM), so the (LTM) form bonds that are harder to break.
Metallic glass alloys can be grouped into two major distinctive categories with intrinsically different corrosion behaviors, namely:
The first group includes the TM-metalloid alloy systems. These alloys are usually the early transition metals (ETM): iron-, copper-, nickel-, cobalt-, zinc-, etc., and late transition metals (LTM): chromium-, zirconium-, titanium-, manganese-, lanthanum-, niobium-, scandium-, yttrium-, etc., base systems, and may normally contain approximately 20 at.% P, B, Si, and/or C as the metalloid component.
The second class consists of binary, ternary or quaternary alloy system such as TM-SM, SM-TM-RE, and assorted SM-TM-X alloys. These alloys can contain a RE and/or TM and SM elements (such as aluminum, magnesium, beryllium, etc.).
2.1. Corrosion and associated mechanisms in the case of the transition metal-metal binary alloys
2.1.1. Fe-based BMG materials
One of the earliest studied systems in metallic glasses (MG), ranging from alloy design to material properties, is that of Fe-base alloys. These alloys can be formed as binary systems, such as Fe-B, or they may be much more complex, such as Fe-Ni-P-B quaternary systems, and even more intricate multiple systems. It has been suggested that the excellent resistance of certain iron metallic glass alloys to both uniform and localized corrosion results from their enhanced chemical reactivity relative to conventional stainless alloys [8]. The resistance to corrosion may be a result of the formation of a kind of passive film consisting of metallic and metalloid elements capable to strengthen the metallic glass surface against any specific chemical attack and under aggressive conditions (cfr. previous chapter).
In addition to the base metal, metallic glass alloys often contain appreciable concentrations of oxide film builder alloying elements to promote passivity, such as Cr, Ni, P, B as in the case of Fe-Ni-Cr-P-B system. They derive their corrosion resistance from similar shielding process as that of crystalline alloys, namely the development of a passive protective film (oxide scales). The significant difference between the corrosion-resistant metallic glass alloys and their crystalline counterparts, such as stainless steels, lies in the fact that the level of chromium necessary to promote passivity can be substantially less in the metallic glass alloys.
2.1.1.1. Effect of Cr content
One of the pioneer corrosion resistance studies on Fe-based amorphous alloys with P and C contents in acid chloride-based solutions was performed by Naka et al. [9]. Both uniform and localized corrosion resistances of these glassy alloys were mainly attributed to the growth of protective oxide films when appropriate additions of C and P are used [10]. A comparison was made between the corrosion rates of crystalline Fe-Cr alloys and amorphous Fe-Cr-P-C alloys as a function of chromium concentration as shown in Figure 1. At low chromium atomic content levels (<4 at.%), the amorphous alloy corrodes at a higher rate than the crystalline material. However, at even higher chromium levels (4 at.%), there is a significant decrease in the corrosion rate of the MG alloy, whereas the crystalline material remains unchanged. At more elevated and intermediate content Cr level (8 at.%), no corrosion was detected on the MG alloy by weight loss experiments after immersion for 168 h. Surprisingly, it was found that the concentration of HCl electrolyte, which has a significant effect on the corrosion behavior of the crystalline alloys, had no effect on the corrosion of the Fe-Cr-P-C or Fe-Ni-Cr-P-C base MG alloy systems, and which exhibited no weight loss after exposure for a period of 168 h [11].
Figure 1.
Comparison of the corrosion rates of glassy FeCrXP13C7 alloys and crystalline iron-chromium alloys in 1 N NaCl solution at 30°C. Reproduced from [11] with permission from Elsevier Science.
Chromium was shown to be very effective to confer pitting resistance, such as for the metallic glass alloys Fe-CrxB13C7 and Fe-CrxB13Si7 in 3% NaCl [8]. With chromium level contents of 2 and 5 at.%, both MG alloy types suffered pitting at potentials more anodic than the free corrosion potential of approximately 0.6 V/SCE. The addition of 8 at.% Cr extended the pitting resistance nearly to 1 V/SCE, which represents an extreme condition of competition for alloys containing such a low level of chromium. By contrast, type 304 stainless steel contains approximately 18 wt.% Cr, yet its pitting potential is several hundred millivolts less positive than that of the foregoing metallic glass alloys.
In another similar study, it has been shown that an increase of the Cr content from 0 up to 16 at.% in a series of Fe-Ni-Cr-P-B MG alloy filaments systems facilitated passivation in acidic electrolyte (1 N NaCl), and no pitting was observed on any of such alloy system polarized below the transpassive potential region [12]. However, polarization at transpassive potentials caused numerous pits to form that penetrated the MG alloy filament surface. Pits were found to be noncrystallographic in shape.
Pang et al. [13] investigated the corrosion behavior of bulk Fe50-XCr16Mo16C18BX alloys (X = 4, 6, and 8 at.%) in HCl solutions. The increase of B level content up to 8 at.% led to a decrease of the passive current density and to the reduction of the corrosion rate as well. Likewise, in other similar corrosion investigations reported elsewhere [13, 14], the Fe43Cr16Mo16C10B5P10 BMG exhibited a lower passive current density than that of Fe43Cr16Mo16C15B10 BMG in a 1 M HCl electrolyte. However, in a 6 M HCl solution, and upon anodic polarization, the current density abruptly increases for the Fe43Cr16Mo16C15B10 BMG, whereas the Fe43Cr16Mo16C10B5P10 BMG displayed a larger region of passive range with a passive current density of 100 mA m−2, which makes it more effective in increasing the corrosion resistance compared to the former. A summary of these findings, which shows a decrease in the passive current density, and the expansion of the passive region as a function of B and P additions to Fe-based BMGs tested either in a 1 M HCl or in a 6 M HCl solution, is displayed in Figure 2.
Figure 2.
Potentiodynamic polarization curves of the cast glassy Fe-based BMGs (rods with a diameter of 1.2 mm) in 1 and 6 M HCl open to air at 298 K. Reproduced from [13, 29] with permission from Elsevier Science.
2.1.1.2. Effect of Mo content
Molybdenum benefits the pitting resistance of metallic glass alloys and crystalline steels. The addition of Mo to glassy Fe-MoxP13C7 alloys suppressed pitting, decreased the critical current density for passivation and the passive current density [15]. As little as 4 at.% Mo prevented pitting corrosion in 1 N HCl; likewise, low additions of Mo were shown to be more effective in decreasing the corrosion rates than Cr. Molybdenum has been shown to facilitate the formation of a passive film of hydrated chromium or iron oxyhydroxide through its enrichment in the corrosion product layer during active dissolution [16]. The enrichment helps for the accumulation of passivating species in the film by lowering the dissolution rate of the species; the Mo-rich product subsequently dissolves, leaving little Mo behind in the film. However, in another case study [17], the increase of Mo content level up to 22.5 at.% was shown to be detrimental to the corrosion resistance of Fe-based BMG, more likely by increasing the risk of formation of secondary phases in the ferritic matrix zone.
2.1.1.3. Effect of other elements content (Ti, Zr, V, Nb, W, Mn, Co, Cu, Ru, Rh, Pd, Pt)
The effect of other alloying elements to Fe-based glass alloy on its corrosion resistance has been addressed in one study [18]. Hence, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, cobalt, nickel, copper, ruthenium, rhodium, palladium, and platinum were all added to the Fe-X-P13C7 glassy alloy [18]. All elements, except manganese, decreased the corrosion rate of the iron glassy alloy in H2SO4, HCl, HNO3, and NaCl solutions. Although the base alloy, Fe-P13C7, did not passivate; additions of any of the foregoing elements at levels from 0.5 up to 40 at.% enabled passivation to occur during anodic polarization in 0.1 N H2SO4. Chromium was the most efficient, still, molybdenum, and titanium were very beneficial. No pitting was observed in 3% NaCl for passivated alloys. The alloys that did not passivate, such as Fe-Co-P13C7, did not pit, but rather they dissolved uniformly.
Fe-W resisted to pitting corrosion up to 2.5 V/SCE in both acidic and neutral chloride solutions (pH 1 and 7, respectively) [19]. Addition of tungsten to Fe-WxP13C7 has the effect of increasing the critical pitting potential, Ecrit, to a level above 2 V/SCE for x = 6 at.%, but when x = 10 at.% of W was added it caused transpassive dissolution at 1 V/SCE of the MG alloy [19].
2.1.2. Ni-based BMG materials
Generally, Ni-based metallic glass systems exhibit a good resistance to uniform and localized corrosion. A number of investigations on the electrochemical characteristics of Ni-based amorphous alloys have been performed on ribbons [20, 21, 22] due to the struggle in producing amorphous bulk samples (i.e., having thickness > 1.5 mm). The elemental constituents that have typically been used to ensure a good corrosion resistance were either additions of metalloids such as P [20, 22] or additions of metals such as Ta [20, 21] and Nb [20].
Metallic glassy Ni-P has been recently investigated, which appeared to resist to chloride-induced corrosion [23]. In fact, its E-log (i) potentiodynamic behavior was basically identical whether in a chlorinated or chlorine-free environment. A form of chemical passivity has been proposed to explain its corrosion behavior. Passivation in the Ni-P system was mainly due to the formation of an ionic barrier layer rather than a classical passive oxide film. This barrier layer consists of hypophosphite ion adsorbed on the nickel phosphorous surface, with hydrogen/H2O bonded outer layer. This barrier reaction layer inhibits the ion transport of water to the surface and thus prevents the hydration of nickel, which is the first step in the nickel dissolution process.
More recently, there have been growing efforts to decrease the additions of P due to its effective action on the loss of ductility of the Fe amorphous alloy [24]. Overall, the strategic approach that is found to be most effective in increasing the corrosion resistance depends on whether the solution is strongly oxidizing or not (e.g., 9 M HNO3).
2.1.2.1. Effect of elements content (Ti, Zr, Ta, Nb, Cr, P)
There has been a consensus that additions of suitable metals to amorphous Ni-based alloys tend to increase their corrosion resistance. The electrochemical behavior of Ni-based amorphous alloys containing Ti, Ta, Zr, Nb, Cr, and/or P has been of a great concern for a number of investigators [20, 25, 26, 27]. One of the most significant studies was led by Shimamura et al. [20] who investigated the effect of P and other valve metals (e.g., Ta) on the corrosion properties of Ni-based amorphous ribbons immersed either in boiling 9 M HNO3 solutions with and without any of Cr6+ ions content or in a boiling 6 M HCl electrolytes. Ta additions have been proven to be the most efficient in lowering the corrosion rates of Ni-based MG alloy. The addition of critical amounts of Ta resulted in undetectable corrosion rates (<10−3 mm year−1). For example, after being immersed in a boiling 9 N HNO3 solution for 168 h, the corrosion rate of Ni60Ti40 was estimated to be close to 1 mm year−1. After adding of 30 at.% Ta, however, the Ni60Ti10Ta30 MG alloy exhibited an immune response to corrosion for the same period of exposure, i.e., 168 h. Immunity was attributed to the formation of a kind of a protective layer. Although, the authors Shimamura et al. [20] claimed that amorphous Ni-Ta alloys required more than 35 at.% Ta in a boiling 6 M HCl solution to form a tantalum oxyhydroxide (TaO2[OH]) shielding passive film.
Alternatively, the addition of a small amount of P to Ni-Ta glassy alloys has been proven to be effective in significantly reducing their corrosion rates. The corrosion rate of Ni70Ta30 in a boiling 6 M HCl solution was more than 104 times greater than that of Ni68Ta30P2 alloy when tested under similar conditions [20]. The authors believed that the addition of P promoted the growth of TaO2(OH) passive film by accelerating selective dissolution of elements unnecessary for the passive film formation [20]. However, when experiments were performed in solutions with a high oxidizing power, the authors found that the addition of P to Ni-Ta alloys was not necessary to promote the growth of the passive film. Interestingly, many research works have suggested that a Ta-enriched passive film would probably be one of the reasons for the high corrosion resistance of Ni-based amorphous alloys in aggressive solutions [20, 21].
Moreover, it has been proven that the addition of approximately of 7 at.% Cr was sufficient to prevent pitting corrosion of Ni-Cr-P-B alloy systems immersed in 10% FeCl3.H2O at 30°C [27]. In another electrochemical study on the Ni-based MG alloy, Habazaki et al. [25] carried out potentiodynamic polarization tests on Ni75-XCrXTa5P16B4 BMGs (X = 5, 10, and 15 at.%) in a 6 M HCl solution in open air at 303 K. The passive current density was shown to decrease as the Cr (at.%) content increased in Ni60Cr15Ta5P16B4.
Not all metal additions can improve the corrosion resistance of Ni-based alloys in aggressive solutions. This was the case for Cobalt. Pang et al. [26] studied the anodic polarization behavior of Ni60-XCoXNb20Ti10Zr10 (X = 0, 5, and 20 at.%) in a 6 M HCl solution. The Co additions did not significantly alter the polarization behavior; however, the three tested compositions exhibited spontaneous passivation in the 6 M HCl solution and no pitting was experienced during the anodic polarization. Passive current densities for the three tested alloys were almost identical, that is, about 102 mA m−2. The beneficial effects behind the modification of Ni-based amorphous alloys are summarized in Figure 3.
Figure 3.
Anodic polarization curves of the bulk glassy Ni60-xCoxNb20Ti10Zr10 alloys with their critical diameters for glass formation and pure niobium, titanium and zirconium in 6 N HCl solution open to air at 298 K. Reproduced from [26] with permission from Elsevier science.
2.1.3. Cu-based BMG materials
Recently, the corrosion behavior of either Cu, Zr, or Cu-Zr glassy alloy systems has been investigated [28]. The potentiodynamic anodic polarization behavior of the alloy system exhibited the characteristics of two components, namely Cu, and Zr, while the corrosion resistance of the alloy was not greater than that of the more passive (and noble) metal of the alloy, viz. zirconium [28]. Thus, it can be deduced that the corrosion resistance in some transition metal-metal alloy systems could seemingly be due to the presence of a key passivation element in the solid substitute solution, and not to the glassy structure.
In line with previous conclusions, and in order to better understand the origin of corrosion resistance in MT-MT systems, another supported corrosion study was carried out on alloys of Cu-Zr and Cu-Ti systems in H2SO4, HCl, HNO3, and NaOH solutions [15]. In all solutions except the alkaline one, that is, NaOH, both crystalline and metallic glass Cu-Ti alloys exhibited corrosion rates lower than those of pure Cu, and in all cases, the corrosion resistance of the metallic glass alloy was better than that of the crystalline alloy. The metallic glass alloys in such compositional systems are not unusually corrosion-resistant; in fact, neither the crystalline nor the glassy forms of the alloys were more corrosion resistant than pure Ti or pure Zr. This may suggest that the presence of passivation elements, such as Ti, or Zr promotes the corrosion resistance of the metallic glass alloys, and therefore it cannot barely be the result of the presence of the glassy or vitreous state. These results are consistent with previous findings in that the corrosion resistance could be determined by the behavior of the most corrosion-resistant component of the glassy alloy in the transition metal-metal systems.
The synthesis of new bulk metallic glass alloys has subsequently extended the field of corrosion study of many alloy systems, including BMGs. Thus, the development of Cu-based BMGs has been a relatively new occurrence. Lin and Johnson [30] have successfully synthesized Cu-Zr-Ti-Ni glassy alloys with thicknesses of at least 4 mm. Afterward, Inoue et al. [31] developed Cu-Zr-Ti amorphous alloys containing at least 50 at.% Cu with critical diameters between 4 and 5 mm. Among the Cu-Ti glassy alloys, the Cu-Zr-Ti [32] and Cu-Hf-Ti [31] BMGs earned more attention because of their excellent mechanical properties (viz. compressive fracture strengths of 2.06–2.15 GPa), which put forward the concept of their possible usage as engineering materials.
The chemical resistance of Cu-BMG systems has become more and more interesting. Unfortunately, the corrosion resistance of most amorphous Cu-based bulk alloys has not been as impressive as their mechanical properties. Nevertheless, the influence of the content of the composition on the corrosion behavior of Cu-based BMGs with a variety of additions of elements is still in a continuous evaluation phase. Many of such additions have shown to improve the corrosion resistance of Cu-based BMGs [33, 34, 35, 36, 37, 39]. Additions of small amounts of Nb [33, 35, 36, 39] led to increase the corrosion resistance of Cu-based BMGs. The alloy with other elements such as Cr [34], Ta [33], or Mo [33, 34, 37] has also proved to be effective in improving the electrochemical properties of the Cu-base BMG systems (e.g., corrosion and pitting potentials, etc.). This was the case of one of the comparative studies conducted by Inoue, and Qin et al. [33, 35, 36], who evaluated the effect of low additions of Nb, Mo, and Ta (to a Cu-Zr-Ti-X (X = Nb, Mo, Ta)) on the corrosion behavior of the Cu60Zr30Ti10 (at.%) BMGs exposed to solutions of 1 M HCl, 1 M HNO3, 1 M NaOH, or 0.5 M (3%) NaCl.
The typical potentiodynamic polarization curves of these Cu-based BMGs are shown in Figure 4. The electrochemical behavior of Cu59.4Zr29.7Ti9.9Nb1, Cu59.4Zr29.7Ti9.9Mo1, and Cu59.4Zr29.7Ti9.9Ta1 demonstrated that the addition of Nb was the most effective element in lowering the corrosion rate of Cu-based systems in all the test solutions considered. An increase in the Nb content (up to 5 at.%) led to a decrease in the rate of corrosion in all the solutions tested. As can be seen in Figure 4, the additions of Nb to Cu-base alloy resulted into more positive values of the Ecor, an indication of the improvement of its nobility, thereby suggesting a better behavior of corrosion resistance. This trend was supported by the lower icor, and the larger Epit values. Ta was not to, as effective as Nb, more likely due to its lower concentration (only 0.2 at.% Ta was added).
Figure 4.
Potentiodynamic polarization curves of Cu-based BMGs (Cu0.6Zr0.3Ti0.1)100xNbx (x = 0, 2 and 6 at.%) alloys) in either 1 N HCl, 0.5 M (3%) NaCl, 1 N H2SO4 or 1 N HNO3 open to air at 298 K. Reproduced from [35] with permission from Elsevier Science.
Liu and Liu [34] investigated the electrochemical behavior of Cu47Zr11Ti34Ni8 and (Cu47Zr11Ti34Ni8)99.5X0.5 (X = Cr, Mo, and W) BMGs in aqueous solutions of 0.5 M H2SO4 and 1 M NaOH. Additions of Cr, Mo, and W have led to the extension of the passive region, the lowering of passive current densities, and lowered the corrosion rates. The alloy with Mo addition, however, showed the most improved corrosion resistance in the two tested solutions, namely H2SO4 and NaOH. All Cu-based BMGs with Mo additions had passive films enriched in ZrO2 and TiO2 but depleted in Cu-oxides, which are less chemically stable and denser than ZrO2 and TiO2 [37]. It was believed that the addition of Mo was most efficient in improving the corrosion resistance of the alloy because its lower ionization energy compared to that of Cr and W, and leading to faster film formation [34, 37].
Attention was paid to the dependence of the corrosion behavior of Cu-based BMGs on the test environment [33, 35, 36, 38, 39]. Different electrolytes have been selected to study this dependency. In their corrosion study of Cu-Zr-Al-Nb BMGs in 1 M HCl, 0.5 M NaCl, or 0.5 M H2SO4, and regardless of the composition, Tam et al. [38] showed that the corrosion rate of Cu-Zr-Al-Nb BMGs was higher in the case of more aggressive solutions (i.e., 1 M HCl and 0.5 M NaCl) and lower in the less aggressive solution (0.5 M H2SO4). In both solutions containing chloride ions, the Cu-BMGs exhibited active behavior, demonstrating the deleterious effects of chloride ions. However, an active-passive behavior was found in the case where Cu-BMGs were exposed to H2SO4. Similarly, Qin et al. [39] showed that either Cu-Zr-Al BMG or Cu-Zr-Al-Nb BMG exhibited an active behavior in a 0.5 M NaCl and escorted with high corrosion rates, and an active-passive response accompanied with low rates of corrosion in 0.5 M H2SO4 solution.
2.1.4. Zr-based BMG materials
So far, there have been only a few attempts to study the electrochemical properties of Zr-based BMGs in recent years. The majority of these studies have been devoted to systems such as Zr-Ni-Cu-Al [40], Zr-Ti-Ni-Cu-Be [41], and Zr-Ti-Ni-Cu [30] alloys. These Zr-based BMG families are attractive due to their good glass-forming ability and excellent mechanical properties.
Since then, the procedure of adding noble elements (e.g., Nb, Pd, Ti, Ta) has enabled it possible to develop new compositions of MG capable of improving both the capacity of glass-forming ability and the resistance to uniform and localized corrosion [42, 43, 44, 45]. Raju et al. [45] investigated the corrosion behavior of Zr-Cu-Al-Ni-X (X = Nb or Ti up to 5 at.%) BMGs in low alkaline sulfate (0.1 M Na2SO4), and chloride electrolytes (0.01 M NaCl). Increasing the Nb or Ti content resulted in a slight decrease in Ecor and an increase in the passive current density in the sulfate solution. On the contrary, such an increase in the contents of Nb and Ti leads to an increase in the values of ηpit and ηp in the NaCl solution, thus revealing the improvement of the alloy vis-a-vis its corrosion resistance. A typical comparative graph of the anodic polarization curves of these related Zr-based BMGs in 0.1 M Na2SO4 electrolytes (pH 8) is shown in Figure 5.
Figure 5.
Anodic polarization curves of Zr-Cu-Al-Ni-x (x = Nb or Ti) BMG alloys in 0.1 M Na2SO4 solution (pH 8). Reproduced from [45] with permission from Elsevier Science.
In a similar study, Asami et al. [42] investigated the electrochemical behavior of Zr60-XNbXAl10Ni10Cu20 (X = 0, 5, 10, 15, and 20 at.%) BMGs in 0.5 M H2SO4 and 1 M HCl solutions. An increase in the concentration of Nb resulted in an increase in the Epit. The ηpit, however, did not always increase when the Nb content was increased. Substitution of 20 at.% of Nb for Zr resulted in a decrease in the rate of corrosion penetration (CPR) in the 1 M HCl solution from 100 down to 1 μm year−1. The effectiveness of Hf addition (at.%) in improving the passivation ability of the Zr-Cu-Ni-Al BMG has been proven by Liu et al. [46]. Nevertheless, it was pointed out that the addition of noble metals does not always guarantee a better corrosion resistance of Zr-base BMGs.
Qin et al. [43] investigated the corrosion resistance of Zr-base bulk amorphous alloys with three different compositions, namely Zr55Al10Cu30Ni5-XPdX (with X = 0, 1, 3, and 5 at.%) in 0.6 M NaCl. Their findings have shown that the additions of Pd to the Zr-based MG lead to a decrease in the value of ηpit. Therefore, a change in the composition of Zr-based BMG does not always have a shielding effect for the MG alloy.
The effect of the environment is as challenging as that of alloying. It has been shown to play a significant role in the corrosion behavior of Zr-based bulk amorphous alloys. Gebert et al. [47] showed that the Zr55Cu30Al10Ni5 exhibited an immune response to localized corrosion either in a 0.1 M Na2SO4 or in a 0.1 M NaOH solution over the entire potential scanning range (−1000 up to 2000 mV/SCE). However, the susceptibility to pitting corrosion was observed on the BMG surface during anodic polarization experiments for chloride concentrations as low as 10−3 M. The Epit was shown to decrease as the chloride concentrations increased. However, this trend has been tempered by the anodic pre-growth of a passive film. Similarly, Mudali et al. [48] have found that an increase in the concentration of NaCl of 0.01–0.2 M, added to a 0.5 M H2SO4 electrolyte, significantly decreased the Epit of the Zr-base BMG. Other studies [47, 49] further support this outcome. It has been shown that a decrease in localized corrosion resistance is appropriately associated with the exposure of the Zr-base BMG surfaces to solutions with increasing concentrations of chloride ions [47, 49]. In agreement with the foregoing conclusions, many researchers [42, 44, 48, 50, 56] have concluded that the majority of the degradation of a number of Zr-based BMG systems due to localized corrosion involved exposure to solutions containing chloride ions while their best performance was satisfied in H2SO4, Na2SO4, and NaOH solutions.
The effect of other factors, despite what has been mentioned above, such as the test temperature and passivation level, was found to affect the electrochemical properties of Zr-based BMGs. Gebert et al. [50] studied this effect on the corrosion behavior of Zr55Cu30Al10Ni5 BMG. The anodic polarization was carried out at 298, 423 and 523 K in a 0.001 M NaCl electrolyte on the pre-passivated Zr55Cu30Al10Ni5 samples and those without any specific treatment. For untreated and pre-passivated BMG samples, the Epit decreases with increasing temperature. It was concluded that a decrease in temperature and prior passivation treatment promoted the tendency of the Zr55Cu30Al10Ni5 BMG to resist pitting in the chloride solution, which was consistent with the observations of many crystalline and amorphous metal systems.
2.2. Corrosion and associated mechanisms in the case of the binary, ternary, or quaternary amorphous alloy systems
2.2.1. Other BMG-based system materials
The majority of previous corrosion studies involved BMG systems based on Cu, Fe, Ni, and Zr, but there are other BMG systems, such as Ca- [51] Mg- [52], and Ti-based MG [53] still under investigation.
The selection of materials and design alloys are, inter alia, the major factors driving the global BMGs market. More new BMG systems will emerge and become commercially available in mass production in the near future as these amorphous alloys have many attractive properties for everyday life such as biomaterials, electronic devices, structures, and so on. This is the case for Ca- and Ti-based BMGs, which have shown great interest because of their potential applications as biomaterials. The Mg-based system is interesting for applications requiring high strength with lightweight materials [54].
The electrochemical properties of Ca-based BMGs (Ca65Mg15Zn20, Ca55Mg18Zn11Cu16, and Ca50Mg20Cu30) were investigated in a 0.05 M Na2SO4 electrolyte [51]. The Ca65Mg15Zn20 BMG experienced pitting at free corrosion conditions and had a CPR of 5691 μm year−1. However, both Ca50Mg20Cu30 and Ca55Mg18Zn11Cu16 were slightly passivated at Ecor conditions and exhibited CPR values in the order of 1503 and 311 μm year−1 respectively.
The electrochemical behavior of the Ti43.3Zr21.7Ni7.5Be27.5 BMG immersed in a phosphate buffered saline (PBS) solution at 310 K was examined by Morrison et al. [53]. The Ti-base BMG exhibited a passive behavior at Ecor conditions but it showed a localized corrosion susceptibility at more increasing potentials. The ηpit value was about 589 mV/SCE. The Ti-base BMG alloy had a CPR value of about 2.9 μm year−1. The authors concluded that the alloy resistance to localized corrosion in the PBS solution was equivalent to or greater than that of the 316 L stainless steel when identical test conditions were prevailed.
Gebert et al. [52] has performed a comparative corrosion study of both Mg65Y10Cu15Ag10 and Mg65Y10Cu25 BMGs in a borate buffer solution (pH 8.4) with pure Mg and Mg65Y10Cu25 crystalline alloys. The electrochemical behavior of both amorphous and crystalline Mg65Y10Cu25 alloys was similar, but superior to that of pure Mg. Although, the Mg65Y10Cu15Ag10 BMG exhibited superior corrosion resistance among the other three alloys.
2.2.2. Corrosion resistance of BMGs in comparison to crystalline alloys
There is still considerable interest in how the electrochemical properties of metallic glasses and BMGs compare to those of conventional crystalline alloys. Amorphous alloys are believed to exhibit corrosion resistance due to:
their compositions, which are not constrained by the solubility limits, and they can be allied to elements promoting passivation [47],
and their lack of microstructural characteristics, such as grain boundaries, dislocations, and precipitates, which commonly serve as sites for the local passive film breakdown entailing pitting.
Comparisons made on amorphous alloys and their crystalline counterparts allowed it possible to determine whether the structural disorder influences their corrosion behavior [55, 56]. Schroeder et al. [55] have shown that the resistance to pitting corrosion of the Zr41.2Ti13.8Cu12.5Ni10Be22.5 BMG was nearly as equivalent as its crystalline counterpart when exposed to 0.5 M NaCl solution. However, the BMG was not more resistant to uniform corrosion in a 0.5 M NaClO4 solution as its crystalline counterpart did. In accordance with this conclusion, Köster et al. [57] showed that there was no significant difference between the polarization behavior of the amorphous and nanocrystalline states of Zr69.5Cu12Ni11Al7.5 in a 0.1 N NaOH. However, Peter et al. [56] have found that the Zr52.5Cu17.9Ni14.6Al10Ti5 BMG exhibited lower corrosion rates and greater resistance to pitting in a 0.6 M NaCl solution relative to their corresponding crystalline alloy of similar composition. Naka et al. [9] reported higher corrosion rates of amorphous Fe70Cr10B20 (ribbon) in a 1 M HCl solution at 303 K relative to the crystalline Fe90Cr10 alloy. Nevertheless, the amorphous Fe50Cr30B20 alloy experienced a lower corrosion rate in 1 M HCl than that of the Fe70Cr30 crystalline alloy. It has been cautioned that a convenient way to make an accurate assessment of the role of structural disorder on the corrosion behavior can only be achieved when the corrosion properties of the amorphous alloy have to be compared to those of a single-phased crystalline alloy of the same composition [58].
When considering the corrosion properties, the effect of the structure must also be addressed. However, the composition of the alloy is more likely to have a much greater influence on the electrochemical behavior of the alloy than if its structure is periodic or in a disordered state [58].
2.3. Tribological and tribocorrosion properties of BMGs
So far, limited literature information is available on the tribocorrosion properties of BMGs. Therefore, a brief overview is given below with respect to the recent major breakthrough in tribological and tribocorrosion performance of BMGs. The evaluation of metallic glasses as potentially applicable in situations where wear and corrosion act simultaneously is still premature.
Among the most important means of characterizing the performance of BMGs, materials scientists opt for the examination of the tribological and/or tribocorrosion resistance of a BMG material. The most studied material systems are zirconium-based bulk metallic glasses (Zr-BMGs) because of their wide use as mechanical components, their simple preparation process, and their excellent properties.
2.3.1. Zr-based BMGs
The tribocorrosion behavior of Zr55Cu30Ni5Al10 BMG sliding against AISI 52100 steel bearing in 3.5% NaCl solution in a pin-on-disk tribometer was evaluated by Ji et al. [59]. The wear volume loss of the Zr55Cu30Ni5Al10 BMG increased as the applied load (up to 20 N), the sliding distance and the sliding velocity (up to 1.5 m s−1) increased. The BMG surface structure was believed to evolve from an amorphous to a pseudo-crystalline nanostructure during sliding wear conditions. Due to the BMG surface crystallization, the wear resistance was improved and the friction coefficient (μ) of the Zr-based BMG-steel tribo-pair decreased from 0.5 to 0.08, but its free corrosion resistance has been lowered. It has also been shown that its degradation mechanisms evolve during sliding-corrosion tests as a function of normal load.
Abrasive wear was the dominant degradation mechanism at a load of 5 N, while adhesive and corrosive wear were predominant for an applied load of 20 N. Compared to AISI 304 stainless steel under similar test conditions, the Zr-based BMG has better tribocorrosion resistance in the NaCl solution but also beneficial in reducing the wear rate of the bearing steel disk. Therefore, the Zr-based BMG could be considered as a good candidate material for tribocorrosion in seawater applications.
2.3.1.1. Effect of the counter-body material
A recent study by Tian et al. [60] focused on the tribological properties of Zr-based BMG sliding against polymers, steels, and ceramics at various loads and speeds. Acoustic emission (AE) technology has been used to analyze the evolution of wear.
The coefficients of friction (μ) of the BMG sliding against either steel or ceramic balls were high (about 0.6–0.85) but decreased with increasing normal load and sliding velocity. As the steel balls were more ductile than the ceramic ones, the steel-BMG tribo-pairs generated weaker AE signals and exhibited larger wear rates. The main wear mechanism of the steel-BMG and ceramic-BMG pairs was dominated by a plastic flow of the BMG surface material caused by structural relaxation. The AE signals in a single frictional sequence decrease slightly with the increase of the sliding velocity due to the elastic energy consumed by the structural relaxation. The wear surfaces of Zr-based BMG samples were smoother, without crushing and peeling due of the super-plasticity of these BMGs over crystalline metallic materials.
Zr-based BMG sliding against polymer balls had much lower and more stable μ (0.5–0.65) than Zr-based BMG sliding against steel or ceramic balls. The low resistance to friction has been attributed to interfacial material transfer of polymer layers to the BMG surface during repeated sliding. The BMG sliding against polymer balls exhibited also the highest AE signals among the three types of counter-body materials considered, indicating that abrasive wear dominated the degradation mechanism in polymer-BMG tribo-pairs. Due to the low hardness and strength of the polymer counter-bodies, the BMG surfaces are not worn off. In addition to the abrasive wear mechanism in polymer-BMG tribo-pairs, a predominant process of adhesive wear was observed when the polymer wear debris (layers) were transferred to the BMG surfaces. Both the worn circular contact area and the wear volume loss of the polymer increased as the sliding distance increased. Similarly, plowing and fracture of the asperities increased after AE signals were found to increase in a single friction sequence. The authors call for the potential application of these types of BMGs in areas where tribology plays an important role. These Zr-based BMGs could act as new alternative candidates for tribo-materials (e.g., counter-body materials) over their traditional crystalline ones.
Zhong et al. [61] studied the tribological properties of Zr41Ti14Cu12.5Ni10Be22.5 pins sliding against different counter-body materials, namely AISI 5120 steel, AISI 52100 steel, and Zr41Ti14Cu12.5Ni10Be22.5 amorphous alloys using a pin-on-disk tribometer at room temperature under relatively heavy loads. The μ depended on the counterbody material. The highest value of μ was measured for AISI 5120 steel (0.30) under a normal load of 150 N, whereas the lowest value (0.15) was recorded for the Zr-based BMG disk for a normal applied load of 100 N. The wear weight loss of the crystalline material disk was lower than that of the pins. The opposite result was obtained when the Zr-based BMG was used as the counterbody material. For the three different counterbody materials, the crystalline disks showed obvious piled-up material without severe peeling-off. In addition, microcracks were found on the AISI 5120 steel disk worn surface, whereas the plastic flow has become one of the dominant wear mechanisms on the AISI 52100 steel disk. However, rough detached surface damage and wave-like patterns accompanied by pronounced delamination have been found on the BMG pins when amorphous disks were used as counterpart. Differences in wear mechanisms have been observed between the crystalline materials and the amorphous disks. The wear mechanisms of Zr-based BMG pins included grooves, micro-cracks, peeling-off and vicious flow when they slid against crystalline materials.
2.3.1.2. Effect of the loading conditions
The tribological behavior of a Zr52.5Cu17.9Ni14.6Al10Ti5 (at.%) BMG sliding against yttria-stabilized zirconia counterparts was investigated using pin-on-disk in two distinct environments, namely air and argon [62]. It was found that the wear of the Zr-based BMG was reduced by more than 45% due to the removal of oxygen from the test environment at two different loads, namely, 16 and 23 N. The surface wear pins were examined using X-ray diffractometry, differential scanning calorimetry, scanning electron microscopy and optical surface profilometry. A number of abrasive particles and grooves were observed on the worn surface of the pin tested in air, while a relatively smooth worn surface was found for specimens tested in argon. In ambient air, an abrasive wear mechanism dominates the degradation mechanism of the BMG pin, whereas, in argon, an adhesive wear controls the wear process.
The effect of the load on the wear behavior of Zr55Cu30Ni5Al10 BMG under linear reciprocating sliding conditions was investigated by Tao et al. [63]. An increase in the normal load results in a decrease of the μ of the Zr-based BMG (from 0.348 down to 0.226), and an increase of the wear volume loss. The wear mechanism evolves during friction, combining different processes such as welding, adhesive, and abrasive wear. At low loads, adhesive wear governs the degradation wear mechanism of the Zr-based BMG.
2.3.1.3. Effect of the test medium
The wear resistance of a Zr61Ti2Cu25Al12 (ZT1) BMG sliding against Si3N4 balls in dry (air), and lubricated states (deionized water, and simulated physiological media) in a ball-on-flat contact configuration was investigated by Wang et al. [64]. It has been shown that the wear resistance of ZT1 BMG in air and deionized water was superior to that of Ti6Al4V alloy but inferior to that of 316 L stainless steel and CoCrMo alloy when similar conditions were used. However, in simulated physiological media, such as phosphate buffered solution (PBS), and DMEM + FBS (Dulbecco’s modified Eagle medium with 10 vol.% fetal bovine serum), the Zr-based BMG exhibited lower wear resistance than that of Ti6Al4V, 316 L stainless steel, and CoCrMo. This was likely attributed to its moderate pitting corrosion resistance, and its poor depassivation-repassivation kinetics, as induced by passive film breakdown in the solution containing chloride ions during the tribo-corrosion conditions. The presence of proteins in the test solution had a significant effect on the rapid decrease in the pitting resistance of the Zr-based BMG, which caused greater and severe wear damage. Therefore, improvement in the pitting resistance of the Zr-based BMG in physiological media is necessary if it concerns its possible use as a biomedical implant. In addition, screening of a good material as a counterpart to coupling with Zr-based BMG is an additional key factor in ensuring better wear resistance (e.g., by lowering its wear rate). In dry conditions, abrasive wear was predominant mechanism in the case of ZT1 BMG. Under lubricated sliding conditions with the presence of deionized water, the wear damage caused by abrasion can be mitigated. In a simulated physiological environment with the presence of chloride ions, synergistic effects of abrasive and corrosive wear more likely control the wear process. For the four metals studied, the wear resistance had no distinct correlation with the hardness, while the material with high Young’s modulus had better wear resistance.
In another investigation conducted by Hua et al. [65], the tribological behavior of a Zr53Al16Co23.25Ag7.75 BMG in air and phosphate buffer saline (PBS) solution was evaluated using ball-on-disk reciprocating sliding contacts. A biomedical alloy Ti-6Al-4V was used for comparison purposes. The wear resistance of the Zr-Al-Co-Ag BMG sliding in air has been shown to be superior to that of Ti-6Al-4V alloy. Under such dry friction conditions, the wear damage on Zr-based BMG was governed by combined oxidational and adhesive wear processes, whereas the wear mechanisms on the Ti-6Al-4V alloy was mainly driven by conjoint processes of abrasion and adhesion damage. Similarly, under lubricated contact conditions, both oxidational and abrasive wear were the main wear mechanisms of the Ti-6Al-4V alloy in PBS. The Zr-based BMG exhibited lower wear resistance under lubricated sliding conditions (i.e., PBS) over dry friction, but higher than that of Ti-6Al-4V alloy. That low wear resistance was likely attributed to the low pitting corrosion resistance of Zr-Al-Co-Ag BMG in the medium containing chloride ions, and to the synergistic effects of abrasive and corrosive wear during the tribocorrosion tests. The pitting resistance in PBS solution of Zr-Al-Co-Ag BMG was lower than that of Ti-6Al-4V alloy, and was considered a key factor in the tribocorrosion behavior of the Zr-based BMG under the conditions considered.
2.3.2. Fe-based BMGs
The sliding wear behavior of a range of rapidly solidified alloy samples based on the composition of Fe68Cr18Mo2B12 (prepared by planar-flow casting) against a cobalt-bonded tungsten carbide counterface was evaluated using a modified crossed-cylinder wear testing rig [66]. A range of microstructures was examined, and the effect on the wear performance was evaluated. Alloys in ribbon forms were investigated in the as-cast amorphous state and after devitrification at various temperatures, and with the bulk-devitrified sample prepared by hot extrusion of the crushed ribbon. Low-temperature crystallization of the ribbon produced a high volume fraction of metastable Fe3B in a ferritic matrix, whereas high-temperature crystallization produced M2B and Mo-rich borides, still in a ferrite matrix. The wear results showed that the alloy having the stable M2B and Mo-rich borides had the best wear performance, whereas that of the amorphous material had the highest wear rate, and the alloy with Fe3B precipitates exhibited an intermediate wear behavior. The wear volume was systematically higher for the amorphous alloy than for the corresponding devitrified material. This was believed to be the result of the continuous crystallization of the glassy ribbon on the worn surface. Crystallization produced a microstructure of deformed ferrite containing a uniform dispersion of very fine boride precipitates. The combination of extensive microcracks and the inability of the precipitates to support the load led to an increase in the wear rate.
3. Toward the use of BMGs for tribo-electrochemistry systems in biomedical applications
The unique properties of BMGs make these materials attractive alternatives in biomedical applications. However, the most promising strategies for biomedical applications are quite limited. BMGs have potential biomedical applications as screws due to their toughness and high strength. Moreover, it has been reported that certain BMG compositions have low magnetic susceptibility, which could be advantageous in surgical instrument applications for interventional magnetic resonance imaging (MRI) [67, 68]. The ease of micro-forming and manufacturing of BMGs [69] also lends itself to the production of gears for small, high-powered micromotors that could be of use in arthroscopic tools. Another promising application is the biofunctionalization technology. Biofunctionalization consists of adapting compounds, for example metals, to make them compatible with a biomedical application. Finally, one of the most promising biomedical applications of BMGs is the use in bone fracture fixation and hip arthroplasty. BMGs have a low modulus that is comparable to the modulus of the bone as well as a high strength to withstand the significant forces generated in the skeletal system of the human body.
In particular, the acceptability of BMGs as potential candidates for implants (e.g., load-bearing materials) in the human body is a very interesting and novel topic for a recent field of applications. To be effective, the BMGs should behave like biomaterials for the duration of their use. Above all, they should have sufficient mechanical strength, corrosion and wear resistance to withstand the harsh conditions of the body environment. If this is not achieved, degradation of the implant occurs and secondary effects take place leading to carcinogenicity, hypersensitivity, inflammation, and other complications. Recent investigations have claimed potential tribocorrosion performance of BMGs in simulated body fluids; however, improvements are needed to achieve full functioning.
The tribocorrosion performance of a Zr-based BMG, namely ZrCuAlNi, has recently been evaluated in different media simulating body fluids with and without the presence of proteins [70]. For comparison, a low-alloyed Zr material and a crystalline structure of the same alloy were also studied. It has been shown that the adsorption of the protein on the metal surface modifies both the cathodic and anodic electrochemical patterns and thus changes the prevailing reactions. The ZrCuAlNi BMG alloy in both structures, that is, amorphous and crystalline, did not form any stable passive film and an active dissolution in the anodic region was observed; only the presence of phosphates has generated a small passive plateau. The results also showed that the BMG material with amorphous structure had the largest wear rates in all electrolytes tested (i.e., NaCl, phosphate buffer solution, and phosphate buffer solution with protein), whereas the crystalline structure of the BMG showed negligible wear rates. Two different tribocorrosion mechanisms were observed in the ZrCuAlNi BMG alloy. The amorphous structure suffered from wear-accelerated corrosion generating larger wear rates due to galvanic coupling effects. The crystalline structure did not suffer from wear accelerated corrosion (no galvanic coupling effects due to lack of passivity) and thus lower wear rates were measured. The amorphous BMG material generated a large amount of wear debris during tribocorrosion tests, which act as very abrasive particles, thereby entailing the wear of the counterpart material (alumina). This was due to the formation of grooves and the growth/breakdown sequences of an amorphous oxide film and the high availability of Zr in the material. Crystalline BMG material generated low amount of wear debris, which could be attributed to recrystallization (nano-crystallization), and the presence of a new intermetallic phase (Zr2Cu), promoting an improvement of its mechanical properties under tribocorrosion conditions.
In another comparable study [71], using a reciprocating ball-on-disk tribometer equipped with an electrochemical cell, the degradation mechanisms due to mechanical wear and tribocorrosion of Zr-based BMGs, with nominal compositions of Zr55Cu30Ni5Al10 and Zr65Cu18Ni7Al10 used as potential load-bearing implant materials, were examined. The Zr65-BMG with a higher Zr content showed an increase in plasticity but a reduction in its wear resistance during sliding was noticed. Both BMGs experienced abrasive wear mechanisms after dry sliding wear test conditions (under applied load of 2 N). The worn surface had a higher hardness and no wear-induced recrystallization was confirmed via FIB cross-section analysis. Therefore, the hardening mechanism was due to the free-volume annihilation under suppressed shear deformation. The more passive nature of the Zr65-BMG had consequently a negative influence on its tribocorrosion resistance since wear-accelerated corrosion speeded-up its governing degradation mechanism. It has been shown that a galvanic coupling established between the depassivated wear track and the surrounding passive area was behind the main degradation mechanism of passive Zr65-BMG subjected to the tribocorrosion environment. In order to apply the BMGs for load-bearing biomedical devices, it is required to find out a balance between their wear-controlled mechanisms, namely wear-accelerated corrosion and static corrosion resistance.
\n',keywords:"bulk metallic glasses, friction, wear-corrosion, synergy, tribocorrosion, tribo-electrochemistry",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/62547.pdf",chapterXML:"https://mts.intechopen.com/source/xml/62547.xml",downloadPdfUrl:"/chapter/pdf-download/62547",previewPdfUrl:"/chapter/pdf-preview/62547",totalDownloads:1117,totalViews:324,totalCrossrefCites:0,totalDimensionsCites:0,totalAltmetricsMentions:0,impactScore:0,impactScorePercentile:39,impactScoreQuartile:2,hasAltmetrics:0,dateSubmitted:"June 6th 2018",dateReviewed:"June 8th 2018",datePrePublished:null,datePublished:"September 19th 2018",dateFinished:"July 10th 2018",readingETA:"0",abstract:"Metallic glasses are relatively new materials with a large potential for applications in various technical and biomedical fields. However, for efficient use of these novel materials with an interesting combination of properties, it is necessary to fully characterize them for their mechanical and electrochemical properties. Studies on the effects of chemical parameters (pH, temperature, concentration of reagent) and tribological parameters (load, sliding speed, counterbody, contact configuration) on the kinetics of the reaction (i.e., the material removal rate) supply information on the dominant mechanisms governing the tribo-electrochemical behavior of metallic glasses. Although considerable efforts have been made to characterize their mechanical, corrosion, and magnetic properties, the study of their tribocorrosion patterns is in a rather unsatisfactory state, and very limited information is available. It is the purpose of this chapter to provide an overview of basic information on the tribo-electrochemical properties of most metallic glasses. This becomes crucial when such materials are to be considered in systems where solid surfaces are prone to mechano-chemical transformation processes.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/62547",risUrl:"/chapter/ris/62547",book:{id:"6726",slug:"metallic-glasses-properties-and-processing"},signatures:"Abdenacer Berradja",authors:[{id:"238628",title:"Ph.D.",name:"Abdenacer",middleName:null,surname:"Berradja",fullName:"Abdenacer Berradja",slug:"abdenacer-berradja",email:"a.berradja@gmail.com",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",institution:null}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Corrosion resistance of bulk metallic glasses",level:"1"},{id:"sec_2_2",title:"2.1. Corrosion and associated mechanisms in the case of the transition metal-metal binary alloys",level:"2"},{id:"sec_2_3",title:"2.1.1. Fe-based BMG materials",level:"3"},{id:"sec_2_4",title:"2.1.1.1. Effect of Cr content",level:"4"},{id:"sec_3_4",title:"2.1.1.2. Effect of Mo content",level:"4"},{id:"sec_4_4",title:"2.1.1.3. Effect of other elements content (Ti, Zr, V, Nb, W, Mn, Co, Cu, Ru, Rh, Pd, Pt)",level:"4"},{id:"sec_6_3",title:"2.1.2. Ni-based BMG materials",level:"3"},{id:"sec_6_4",title:"2.1.2.1. Effect of elements content (Ti, Zr, Ta, Nb, Cr, P)",level:"4"},{id:"sec_8_3",title:"2.1.3. Cu-based BMG materials",level:"3"},{id:"sec_9_3",title:"2.1.4. Zr-based BMG materials",level:"3"},{id:"sec_11_2",title:"2.2. Corrosion and associated mechanisms in the case of the binary, ternary, or quaternary amorphous alloy systems",level:"2"},{id:"sec_11_3",title:"2.2.1. Other BMG-based system materials",level:"3"},{id:"sec_12_3",title:"2.2.2. Corrosion resistance of BMGs in comparison to crystalline alloys",level:"3"},{id:"sec_14_2",title:"2.3. Tribological and tribocorrosion properties of BMGs",level:"2"},{id:"sec_14_3",title:"2.3.1. Zr-based BMGs",level:"3"},{id:"sec_14_4",title:"2.3.1.1. Effect of the counter-body material",level:"4"},{id:"sec_15_4",title:"2.3.1.2. Effect of the loading conditions",level:"4"},{id:"sec_16_4",title:"2.3.1.3. Effect of the test medium",level:"4"},{id:"sec_18_3",title:"2.3.2. Fe-based BMGs",level:"3"},{id:"sec_21",title:"3. Toward the use of BMGs for tribo-electrochemistry systems in biomedical applications",level:"1"}],chapterReferences:[{id:"B1",body:'Kramer J. The amorphous state of metals. Zeitschrift für Physik. 1937;106:675-691'},{id:"B2",body:'Brenner A, Couch DE, Williams EK. Electrodeposition of alloys of phosphorus with nickel or cobalt. J. Research of the National Bureau of Standards. 1950;44:109'},{id:"B3",body:'Klement W, Willens RH, Duwez P. Non-crystalline structure in solidified gold-silicon alloys. Nature. 1960;187:869-870'},{id:"B4",body:'Naka M, Hashimoto K, Masumoto T. Corrosion resistance of amorphous iron alloys with chromium. J. 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Journal of Non-Crystalline Solids. 2015;426:63-71'},{id:"B66",body:'Anis M, Rainforth WM, Davies HA. Wear behaviour of rapidly solidified Fe68Cr18Mo2B12 alloys. Wear. 1994;172(2):135-145'},{id:"B67",body:'Seifert V, Zimmermann M, Trantakis C, Vitzthum HE, Kuhnel K, Raabe A, Bootz F, Schneider JP, Schmidt F, Dietrich J. Open MRI-guided neurosurgery. Acta Neurochirurgica. 1999;141:455-464'},{id:"B68",body:'Horton JA, Parsell DE. Biomedical potential of a zirconium-based bulk metallic glass. MRS Proceedings In: Symposium CC- Supercooled Liquids, Glass Transition and Bulk Metallic Glasses; Vol. 754, CC1.5; 2002. DOI: 10.1557/PROC-754-CC1.5'},{id:"B69",body:'Saotome Y, Hatori T, Zhang T, Inoue A. Superplastic micro/nano-formability of La-60, Al-20, Ni-10, Co-5, Cu-5 amorphous alloy in supercooled liquid state. Materials Science and Engineering A. 2001;304-306:716-720'},{id:"B70",body:'Espallargas N, Aune RE, Torres C, Papageorgiou N, Muñoz AI. Bulk metallic glasses (BMG) for biomedical applications—A tribocorrosion investigation of Zr55Cu30Ni5Al10 in simulated body fluid. Wear. 2013;301(1-2):271-279'},{id:"B71",body:'Zhao GH, Aune RE, Mao H, Espallargas N. Degradation of Zr-based bulk metallic glasses used in load-bearing implants: A tribocorrosion appraisal. J. Mechanical Behavior of Biomedical Materials. 2015;60:56-67'}],footnotes:[],contributors:[{corresp:"yes",contributorFullName:"Abdenacer Berradja",address:"a.berradja@gmail.com",affiliation:'
MTM Department, K.U. Leuven, Leuven, Belgium
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1. Introduction
Calorimetry is the experimental technique that allows the determination of the heat transferred between two systems with different temperatures. Basically, it can be applied to obtain the specific heats of the substances, as well as the heats of phase transitions and formation/decomposition processes. The accuracy of the assay of the abovementioned parameters depends on the accuracy of the mass and temperature measurements and the purity of the investigated samples. Sometimes it is necessary to estimate the specific heats for hypothetic materials or materials that are expensive, difficult to synthesize or dangerous for humans and environment. For such cases the heat capacity can be estimated by thermodynamic calculations using the enthalpies and entropies from the thermodynamic databases for pure materials, as in the CALPHAD method. An alternative way, especially when the databases do not contain usable information, is to use the computing methods that can predict the total energy and the vibrational frequencies of a given system. The density functional theory (DFT) is an electronic structure method that considers the electron correlation at a low computational cost and provides accurate results. The high-quality calculations of the vibration frequencies for periodic and nonperiodic systems in various approximations (harmonic, quasiharmonic, and anharmonic) support the calculation of the thermodynamic properties (enthalpy, entropy, and Gibbs free energy) for different composition, pressure P, and temperature T conditions, which can be used to calculate the heat capacity.
In this chapter, we present the theoretical basis of the thermodynamics approach of the heat capacity for crystals for given thermodynamic conditions P and T based on the DFT calculations, having as example six polymorphs of the magnesium hydrides, which are reported in Ref. [1] where the assessments of the thermodynamic properties and pressure–temperature phase diagram of the magnesium hydride polymorphs are done.
Several polymorphs of magnesium hydride were experimentally identified and validated by several electronic structure calculations [1, 2, 3]. The knowledge of the various MgH2 phase stability has led to an increase in research regarding the pressure–temperature phase diagram for the magnesium hydride. Under ambient conditions, the magnesium hydride crystallizes as α-MgH2 phase, with a rutile-type structure (space group P42/mnm) [4]. Bastide et al. found that under high pressure and temperature conditions, the α-MgH2 structure is transformed into β-MgH2 (space group Pa-3) and γ-MgH2 (space group Pbcn); by decreasing the pressure, the β-MgH2 is transformed into γ-MgH2 [5].
The magnesium hydride P–T phase diagram based on the thermodynamic calculations [1] shows that in the pressure range 0–1.5 GPa, the α-MgH2 phase is the most stable and that the γ-MgH2 is stable below 6.2 GPa. Above this value, the ε-MgH2 becomes the most stable up to 10 GPa, the maximum pressure considered in the study. However, in the region of 5.5–7.5 GPa, with exception of the cubic phase c-MgH2, all the investigated magnesium hydrides might coexist, since their enthalpies have similar values. The hypothetic c-MgH2 polymorph is the less stable phase, excepting the interval of 0.0–0.4 GPa, where it has enthalpy values comparable with the ε-MgH2 phase. The cubic polymorph was identified in an experiment as metastable nanocrystals, which transform to γ- and α-MgH2 [6]. In a subsequent study [7], we predicted that the formation/decomposition curve over all polymorphs is starting from 591.1 K for the low-pressure P = 0.03 GPa, growing with the applied pressure.
The theoretical framework for the thermodynamic calculations presented in the present chapter of the book can be extended to nonperiodic systems (defects, surfaces, interfaces, alloys, amorphous, fluids, and isolated molecules) still using the periodic formalism, but modeling the system in the supercell method, or finite systems (molecules and macromolecules, clusters), where the molecular orbital formalism (specific to the quantum chemistry, which is proper to the isolated systems) is used instead of the crystal orbital formalism (specific to the quantum solid state). For the finite systems, the contributions of the rotation and translation freedom degrees have to be added to the partition function and the free energy of the system.
2. Total energy computation methods
The computer-assisted simulations of the particle systems require: (i) a model for the system, which specifies the chemical species, the position in space (given in Cartesian, internal, or redundant coordinates) and, in case of dynamic treatments, the velocity of each particle; (ii) the method that describes the interactions between the particles and different parameters regarding the calculation method; (iii) different parameters that describe the simulation method (threshold parameters, calculation schemes, and eventually the parallelization technique); and (iv) the parameters and properties that have to be reported by the simulation software.
An ideal crystal can be represented as an indefinitely extended lattice that can be obtained by the translation of a repeated parallelepipedic box, called unit cell. The unit cell is populated with a set of atoms (called atomic basis) that may be arranged in some special points characterized by a set of symmetry operations that is specific for each polymorph of a crystalline substance. The unit cell is characterized by the lengths and mutual orientations of three lattice vectors that delimit the unit cell shape. The solid-state physics is the science that characterizes and classifies the crystals and tries to establish a relation between the nature of the atoms, the structures formed by them, and the crystal properties. The infinite crystal is reduced to the study of the properties of the unit cell, the smallest piece of crystal that preserves the properties of the entire system. The crystals have some local or extended defects, but without losing their global ordering. The crystalline materials can be built based on the experimental structural data that are collected in several online databases or trying to predict it by molecular mechanics and ab-initio calculations. The symmetry of the periodic systems (1D for polymers, 2D for surfaces or films, and 3D for solids) can be used to reduce the computation effort [8].
The equations of state of a given system are obtain by successive approximations having as starting point the time-dependent or the—independent Schrödinger equation associated to electrons and nuclei that form the system. The relativistic contributions to total energy are important for heavy chemical elements and must be considered at least as a perturbation. Due to the relative light mass of the electron compared with the mass of the nuclei, movement of the nuclei and electrons is separated in the frame of the Born-Oppenheimer approximation. The approximation is suitable when the electrons wave function gradient depending of nuclei positions has very small values. The Born-Oppenheimer approximation is not valid when energy values of different electronic states are very close in energy at some nuclear configurations.
For the finite systems (atoms, molecules, clusters) the mono-electronic wave function φir→=∑μ=1ϖcμiχμr→ is developed in analytic or numeric basis sets χμr→, and thus the complex equations are transformed in some treatable ones. In the Linear Combination of Atomic Orbitals (LCAO) approach [9], the functions χμr→ are atomic orbitals, and the amplitude of the coefficients cμi can be used to interpret the interaction in the system. The radial part of the AO might have different mathematical representations (Slater-type, Gaussian-type, or numeric atom-centered orbitals). In the LCAO approach, the parameters can be decomposed into atomic orbital contributions that can be used to interpret the interaction in the system. The wave functions are called Molecular Orbitals and the corresponding theory, Quantum Chemistry.
For a periodic system (crystal, slabs, surfaces, wires, and tubes), the Born-von Karman boundary condition introduces the expansion of physical quantities to Fourier series. To simplify the solving of the mono-electron Schrödinger equation, the Bloch theorem exploits the translation symmetry of the system and implicitly of the potential, by factorizing the mono-electron wave function as φir→→φnk→r→=eik→r→unk→r→, where k→ is a vector defined in the reciprocal space, and n is the band index. Thus, the Bloch theorem indicates the way to reduce the computing of an infinite number of electronic wave functions to a finite number of electron wave functions, as well as the indexation of the electron wave functions by the band index n. The wave functions are called Crystal Orbitals (CO) and the corresponding theory, Quantum Solid-State.
By solving the reduced mono-electronic equation for each k→, a set of energies ∈nk→ is obtained. By using the periodicity of the reciprocal space, a polyhedron called Brillouin zone (BZ) may be defined in the reciprocal space. The wave vectors outside the Brillouin zone simply correspond to states that are physically identical to those states within the BZ. For each band n, the energy levels ∈nk→ evolve smoothly with the changes in k→, forming a continuum band of states. The electronic wave functions for closed k→-points are very similar, and the integration in the reciprocal space can be reduced to a summation over a grid of k-points [10]. The integrals over k-space converge exponentially with the number of sampling k-points and several recipes are available to compute the sets of spatial k→-points for different symmetries in order to accelerate the convergence of BZ integrations were developed [11]. Due to the partial filling of the energy bands in the case of the metals, the BZ is discontinuous. In this case, the calculations of the integrals over BZ with a denserk→-grid and the broadening of the electronic levels may reduce the magnitude of the errors [12].
The development of the electronic functions using a plane wave (PW) basis set unk→r→=∑G→=1∞cG→ink→eiG→r→ is a natural choice for the crystals, as the equations obtained are very similar with those of Nearly Free Electron model [13]. Therefore, the mono-electronic wave function may be written as φik→r→=eik→r→unk→r→=∑G→=1∞cG→ink→eik→+G→r→. The different terms of the total energy are written as Fourier transforms, thus simplifying the numerical treatments. For the periodic systems, the use of a plane wave basis set in the description of the COs offers a number of advantages, including the simplicity of the basis functions, the absence of basis set superposition error, and the ability to calculate efficiently the forces acting on the atoms. In case of the ionic crystals, the PW method is not efficient because of the high number of plane waves that are required for an accurate description of the wave functions near the ionic core.
Only the electrons that occupy the high energy levels (called valence electrons) are responsible for formation and breaking of the chemical bonds and for the interaction with the low-energy radiation. The rest of the electrons (called core electrons) generally are not affected by the chemical environment and are not as significant as the valence electrons. Thus, treating explicitly only the valence electrons, a further decrease of the computational effort can be achived. The core electrons are emulated by effective core potentials (ECPs) in quantum chemistry LCAO methods or by pseudopotentials (PPs) in the solid-state PW methods [14]. Thus, only the valence electrons are considered in the electronic equations [15]. The core potentials are developed so as to reproduce the energies, as well as the wave function amplitude (outside of a given cutoff radius) of the atomic core wave functions. The PPs that satisfy the condition of the normalization outside of the cutoff radius are called norm-conserving pseudopotentials (NCPP) [16], and those for which this condition is relaxed are called ultrasoft pseudopotentials (USPPs) [17]. The PPs allow one to perform the calculations at a lower energy cutoff. The USPPs are less computationally expensive in comparison with NCPP. For the heavy elements, the relativistic effects can be incorporated in the ECP/PP [18].
2.1 The simulation methods for the electronic ground states
From a broad palette of electronic structure methods, the quantum methods based on the Hartree-Fock Theory (HFT) [19, 20] and the Density Functional Theory (DFT) [20] are the most popular and mostly used. The neglect of the electron correlation in HFT affects the quality of the results, especially the energy-derived properties. The influence of the electron correlation on the band structure and on the cohesion energy in the oxide materials has been the object of a huge number of articles. The electron correlation effects are important for the ionic crystals, as the electron density is localized in a reduced domain around the ionic core. The existing post-Hartee-Fock correction schemes based on the Configuration Interaction, Coupled Cluster Theory, or Møller-Plesset Perturbation Theory are very accurate [21], but too expensive from a computational point of view to be applied to large systems. Some technical difficulties make them very rare in the solid-state software. Fortunately, the methods based on the DFT are good alternatives. In DFT, the total energy is expressed in terms of total electron density, rather than the many-electron wave function specific to HFT. The choice of the exchange-correlation potentials is a matter of trial and error in the DFT, as the method itself does not provide an explicit dependency of the exchange-correlation potentials on the electron density. Developed initially based on the model of the uniform electron distribution in the Local Density Approximation (LDA), the accuracy of the DFT was increased after including additional corrections that consider the variation of the density in the Generalized Gradient Approximation (GGA). Despite the numerous improvements of the DFT methods on the top of GGA (Self-Interaction and Hubbard U corrections, meta-GGA, and hybrid functionals) [22] regarding the overestimation of the band gap for the semiconductors, there are still efforts to find transferable correlation-exchange potentials. The various proposed exchange-correlation potentials do not describe well the weak van der Waals interactions between the two chemical systems. The simplest solution is to treat the dispersion interaction adding an analytic empirical term of London type to the total energy [23].
Due to the similarity of the Hartree-Fock and Kohn-Sham equations, several electronic structure codes work within the framework of both HFT and DFT and can treat the exchange interaction in a hybrid scheme, incorporating the full or partial Fock exchange in the DFT calculations. Both methods can separately treat the two spin orientations up and down of the electrons, in so-called Unrestricted HF in HFT and spin-polarized or spin-density calculations in DFT. This double framework approach allows the study of the electron correlation effects in 0d-3d periodical systems in a unified way.
The several approaches can be applied in order to reduce the calculation effort by approximation of the integrals by simpler formulas or just parameterization as in the Extended Hückel and various Zero Differential Overlap methods [24] in the frame of the HFT or Density Functional Tight Binding (DFTB) in DFT. These methods are called semiempirical methods, as they contain some empirical determined parameters. Generally, the semiempirical methods consider only the valence electrons, the effects of the core electrons being included in the parameterization of the method. The computational effort required by the semiempirical methods is significantly reduced comparing with the ab-initio methods due to the drastically simplification of numeric calculations and of the great reduction of the considered number of electrons. The prices that must be paid are the reduced accuracy and the reduced transferability of the parameters to other chemical systems that those used for parameterization. However, the semiempirical methods can be used as tool for the pre-selection of the materials that can be investigated in the high-throughput computational screening techniques.
In order to further reduce the calculation efforts, the interaction between atoms can be represented by analytical formula developing so-called the empirical force fields (EFFs), where usually the electrons are not explicitly considered. Thus, the electronic freedom degrees are eliminated, and the computing effort is drastically reduced to square of the total number of particles. Further reduction of the number of the freedom degrees can be done by partly or total freezing of the internal geometry of molecules. The parameters of EFF can be obtained by fitting the total energies and forces calculated by ab-initio electronic structure methods [25]. Also, the phonon properties have to be included into the parameterization procedure as reference data for accurate calculations of the thermodynamic properties [26].
2.2 The simulation methods for the electronic excited states
Neither HFT nor DFT is able to treat the electronic excitation and to characterize the electrons in the excited states. The HFT applied to the excited states is equivalent to the electron configuration methods for the ground state. The DFT is constructed based on the ground electronic density and cannot be directly extended to the excited electronic states. The use of multi-reference and the perturbative correlation interaction methods over the Hartree-Fock wave functions is able to characterize the excited states, but they cannot be applied to large systems because of the high computational efforts. Moreover, such methods require very large basis sets, which drastically increase the size of the CPU memory that is necessary to store very large matrices. There are trials to correct for the excited states, the DFT-determined states with the Configuration Interaction [27], Random-Phase Approximation [28], or Machine Learning [29], but such methods are not implemented in the available quantum chemistry or solid-state software.
A more natural approach is to start from the excitation process by the electromagnetic field as an external field. Thus, the HFT and DFT must be reconsidered in the frame of the time-dependent Schrödinger equation. In the case of DFT, an analogous equation to the static Kohn-Sham theorem that states that any expectation value is a functional of the density, and the initial state is established. This formalism is called Time-Dependent Density Functional Theory (TDDFT) [30]. TDDFT has the same problem like the static DFT as the exchange-correlation potential is not defined. The adiabatic approximation treats the exchange-correlation kernel as static, which permits its evaluation from the derivative of the ground state exchange-correlation potential with respect to the density. The simplest choice is the Adiabatic Local Density Approximation, in which the exchange-correlation kernel is calculated from the ground-state LDA functional [31].
The excited electron and the local environment of the electron (hole) behave like a collective excitation called pseudoparticle, which could be treated in the Many-Body Perturbation Theory (MBPT) and the Green’s function formalism. The GW formalism uses an similar equation to Kohn-Sham equation that governs the energy and the wave functions of the quasiparticle, only that the exchange-correlation potential is replaced by an integral over the self-energy operator that incorporates all the electron–electron interactions [32]. The mean field is determined from DFT calculations and is used to calculate the GW interaction terms. When in GW only the energy of the quasiparticle is modified, but the wave function is kept unchanged, then the method is simplified (so-called G0W0), and the energy of the quasiparticle is obtained as a first-order HF or KS energy. The corrected energies in the G0W0 method give accurate band gaps for semiconductors or insulators. The introduction of the self-consistency within GW gives better band gaps than G0W0, but with a much higher computational effort. The use of the hybrid functionals for calculation of the initial wave functions is desired, but the GW calculations are very expensive, and thus, the application is limited to the small systems. There is some improvement of the algorithms that allow application of GW method to large systems. The GW approaches can be applied to the neutral excitations, but are not able to consider the charged excitations. The Bethe-Salpeter equation (BSE), which is based on the two-particle Green’s functions and the effective two-particle interaction kernel, solves the shortcoming [33]. The kernel can be expressed as sum of the derivatives of the Hartree potential function on the self-energy calculation in GW method. The GW and BSE methods predict more accurately the excitation energies and absorption spectra, compared with DFT methods [34]. Unfortunately, the computational effort increases drastically in the order DFT < GW < BSE. For large systems (more than few hundreds of atoms), even the DFT calculations are prohibited. The semiempirical methods with an accurate parameterization [35] can be applied at reduced computational efforts for large systems in the ground [36] or excited states [37].
2.3 Static and dynamic properties
Total energy is dependent on the relative arrangement of the atoms. Changing continuously the position of the atoms, the energy is continuously modified, and this function energy – coordinate is called potential energy surface (PES). The configuration of atoms that are characterized by minimum or maximum values of the system energy corresponds to an equilibrium or transition states, respectively. Such atomic configurations can be determined by using some mathematical methods that modify the position of the atoms in order to minimize or maximize the total energy, preferentially using the first and second derivatives of the total energy. The derivatives are obtained analytically or numerically. The energy and its derivatives calculated by the electronic structure methods can be used as reference data in the empirical force fields parameterization, in order to reproduce the static and dynamics properties of the atomic systems [38]. The static calculations are very useful to characterize the stability, elastic and electronic properties, the vibration spectra and the thermodynamic properties, and the way of transition from a structure to another.
Ehrenfest theorem establishes the theoretical basis for time evolution of a quantum system. Due to nuclei large masses, the Ehrenfest theorem can be reduce to Newton equation, which rules the atoms movement on the PES. The theory that describes the system time evolution is called Molecular Dynamics (MD). The dynamic properties of the investigated system can be accessed through the MD simulations, which consist of the integration of the Newton equation of each atom of the system. The forces that act on the atoms can be evaluated from electronic structure calculation or can be evaluated by much cheaper empirical force fields. Besides total energy minimization, MD simulations allows the simulation: (i) of the behavior of atoms that form the system (ii) of any kind of chemical species using empirical and quantum force field (iii) of the different statistical ensembles. After saving the trajectories in files and data process, we can: (i) visualize the dynamic of the system; (ii) plot and analyze temperature, pressure, distances, volume, tensile forces, and cell parameters; (iii) calculate velocity correlation factor and vibration intensities; (iv) calculate radial distribution functions and structure factors; (v) calculate various thermodynamics parameters in different thermodynamic ensembles [39].
PES structure and system thermodynamics can be characterized by the heuristic methods and data averaging, which describe the system by very large number of attempts. The most common method is Monte Carlo (MC) based on random-walk movement on PES. The sequences of the events are not related with the time evolution of the system as in case of the MD; they are rather dependent on the chosen algorithm. Because the time evolution of the system is not considered, the MC simulation cannot describe the nonequilibrium processes. Time independence can be an advantage for processes that are taking place on a large timescale or in case of PES with a high “roughness.”
2.4 Equation of states and pressure
The calculation of accurate equations of state (EOS), thermodynamic properties, and phase diagrams is a very useful tool in a number of fields, including geophysics [40] and materials research [41]. One of the main advantages of the calculation of pressure and temperature-dependent crystal properties is the ability to investigate the extreme thermodynamic conditions, unattainable by experimental means. Indeed, provided that there are no technical difficulties (e.g., pseudopotential transferability issues [42]), pressure effects can be accounted for simply by compression/expansion of the calculated crystal geometry to smaller/larger volumes compared with the equilibrium volume.
In the present study, the DFT calculations are based on plane waves basis sets techniques combined with ultrasoft pseudopotentials and were carried out with the Quantum Espresso (QE) package [43]. The thermo_pw package [44] was used to obtain the thermodynamic properties within harmonic and quasi-harmonic approximations. The PBE-GGA [45] exchange-correlation potentials were used in the calculations. We have chosen computational settings to ensure that all investigated properties are well converged. The kinetic energy cutoff was set to 55–60 Ry while the charge density cutoff was set to 300 Ry. The integration over the Brillouin zone (BZ) was performed employing a Monkhorst–Pack mesh with a spacing of 0.04 Å−1, as a good balance between the calculation accuracy and the computational effort. The total energy of the polymorphs of the MgH2 has been minimized function with respect to the unit cell parameters and fractional coordinates of the atoms, preserving the symmetry of the crystal.
The equilibrium volume V0 and the corresponding energy U0 can be determined by a full optimization of the lattice parameters and atom fractional coordinates. Furthermore, the volume dependency of the unit cell UV can be obtained by scaling the lattice constants with the same factor (isotropic procedure) and calculating the corresponding energy U(V). The minimum of the curve corresponds to the equilibrium point (V0,U0). The curve can be fitted by the Murnaghan Equation of States (EOS) [46], which relates by a simple polynomial equation the volume Vand its equilibrium value V0, the bulk modulus B=−V∂P∂VT and its derivative B\'=∂K∂PT by
UV=U0+B0VB\'V0/VB\'B\'−1+1−V0B0B\'−1E1
More complex EOSs are available in the literature (see the citations in Refs. [47, 48]), but their qualities are similar. The dependence of the energy on the unit cell volume obtained for the different magnesium hydride structures is presented in Figure 1. The obtained values of the parameters U0, B0 and B\' by fitting the EOS given by Eq. (1) are presented in Table 1. The minimum of the curves gives the equilibrium volume V0 and the equilibrium energy U0, which are identical with those calculated by a full optimization (lattice parameters and fraction coordinates of the atoms) and are in very good agreement with the experimental values (see Table 1 in Ref. [1]).
Figure 1.
The energy vs. volume for the polymorphs α, β, γ, δ, ε and cubic of the magnesium hydride obtained by an isotropic procedure. The dependency energy-volume determined by an anisotropic procedure is given for the polymorph α-MgH2.
Polymorph of MgH2
Symmetry group
MgH2 formula unit (f.u.) per unit cell
Total energy U0 (Ry/f.u.)
Electronic smearing term (Ry/f.u.)
Equili-brium volume V0 (Å3)
Bulk modulus B (GPa)
B´
Debye tempe-rature (K)
α (isotropic)
P42/mnm
2
−143.5961
0.0014
62.50
51.1
3.59
707.4
α (anisotropic)
P42/mnm
2
−143.5961
0.0014
62.48
58.3
4.65
691.2
β
Pa-3
4
−143.5902
0.0002
113.67
54.6
2.48
699.9
c
Fm-3 m
1
−143.5734
−0.0004
27.55
63.7
1.00
511.2
δ
Pbca
8
−143.5880
0.0000
222.23
57.8
1.60
739.9
ε
Pnma
4
−143.5801
0.0000
101.48
61.12
4.10
627.5
γ
Pbcn
4
−143.5966
0.0001
123.15
47.5
3.48
717.7
Table 1.
The properties of the investigated polymorphs of the MgH2 obtained from the Murnaghan equation of state. For the polymorph α-MgH2, the values are presented both for the isotropic and anisotropic volume adjustments. The total energy was corrected by cold smearing procedure, included in Quantum espresso code.
At low temperatures, the system energy is only dependent on the system volume, and the pressure can be estimated by
PV=−dEdV=B0B\'V0VB\'−1E2
A special care has to be paid when the dependency of energy versus volume is determined in the case of the non-cubic systems, where the lattice parameters and fractional coordinates of the atoms must be optimized for each value of the volume, in order to assure that the energy has the minimum value. Such calculations are done on a grid of lattice parameter under the constraint of a given value of the volume, and those lattice parameters that assure minimum energies are identified. In order to check the effects of the lattice relaxation, we determined the U(V) dependency for the polymorph α-MgH2 by scaling the lattice constants with the same factor (isotropic procedure) and by a lattice-grid calculation (anisotropic procedure). In the isotropic procedure, nine equidistant scaling factors of the volume between 0.80 and 1.20 were considered. In the anisotropic case, a grid 5 × 5 of a and c/a, centered at the equilibrium values, with steps of 0.05 Å and 0.02, respectively, was considered. The energy was fitted with quartic polynomials as a function of a and c/a and the pairs (a,c/a) for which the energies have a minimum were identified. The results of the Murnaghan fit are given in Table 1 and Figure 1. It can be seen that in case of α-MgH2, the isotropic and anisotropic U(V) essentially have the same behavior around the equilibrium volume V0. The same trend also was observed for the other non-cubic polymorphs of the MgH2.
3. Phonon calculations in lattice dynamics method: Harmonic approximation
The crystal potential energy can be expanded as a Taylor series [49] by small displacements uα,mI from their equilibrium positions of the atoms I located in the unit cell m, along the Cartesian direction α=x/y/z, as
U=Uo+U1+U2+U3+…E3
where:
U0- is the static energy of the system in the equilibrium geometry,
U1=∑mIαΦmIαuα,mI=0- is zero as the system is in the equilibrium geometry.
The other terms are the n-body crystal potentials (n = 2, 3, …). The second- and the third-order potentials are
U2=12∑mIα∑lJβΦmI,lJαβuα,mIuβ,lJE4
U3=16∑mIα∑lJβ∑nKγΦmI,lJαβγuα,mIuβ,lJuγ,nKE5
where ΦmI,lJαβ and ΦmI,lJαβγ are the harmonic and cubic anharmonic force constants, respectively.
Limiting the expansion to second term, we have the harmonic approximation, which is the fundament of the vibrational frequencies calculations. The reduced HamiltonianHHA=12∑mIαmIu̇α,mI2+U2, which includes the kinetic energy of the atom I with the mass mI, is the harmonic Hamiltonian of the system. The problem of Na atoms per unit cell that moves in a periodic potential is separable and can be solved exactly by diagonalization of the equation of the eigenvalues and eigenvectors
∑β,JDIJαβq→eβ,Jq→j=ωq→,j2eα,Iq→jE6
of the dynamical matrix
DIJαβq→=1mImJ12∑lΦ0I,lJαβeiq→r→lJ−r→0IE7
The solutions ωq→,j and eα,Iq→j are the frequency and polarization vector that correspond to the phonon normal mode of band index j and wave vector q→ in the Brillouin zone. The matrix DIJαβq→ is a hermitic one and its eigenvalues have to be positive. However, sometimes the normal modes might have negative eigenvalues, which correspond to imaginary frequencies. In such a case, the energy decreases along the eigenvector eα,Iq→j and the system becomes unstable.
The phonon frequencies for a unit cell in equilibrium (i.e., the energy is minimized and there are no forces on atoms and no stress in the unit cell) can be calculated from the derivative of the energy (phonon freeze method) [50] or considering the forces of each atom in the frame of the linear response method (Density Functional Perturbation Theory—DFPT) [51]. The phonon occupation number at the equilibrium is given by the Bose-Einstein distribution nq→,j=expℏωq→,j/kBT−1−1. At absolute zero temperature, the phonon population is zero, at low temperatures, there is a small probability for the phonons to exist, and at high temperatures, the number of phonons increases with temperature. The maximum number of phonon modes is given by the maximum number of freedom degrees 3⋅Na, where Na is the total number of atoms in the unit cell of the crystal.
The relation between ωq→,j and q→ for each mode j, namely ωj=ωjq→, is called phonon dispersion. The number of the phonon modes with the frequency between ω and ω+Δω gives the phonon density of states gω=1/N∑q→,jδω−ωq→,j, where N is the number of unit cells in the crystal. The normalization factor 1/3⋅Na is introduced in order to reduce to 1 the integral of gω over frequency ∫gωdω=1.
The DFPT method [51], implemented in the module thermo_pw code [44], was used to calculate the phonon spectrum for the MgH2 polymorphs for each of the volume values on a 6 × 6 × 6 grid of q→-points and Fourier interpolated in the Brilloun Zone. The phonon density of states (DOSs) are computed by integrating the phonon dispersion in the q→-space. We present in Figure 2 the phonon band structure and DOS for the polymorph α-MgH2. The phonon spectra are similar with the one obtained by inelastic neutron scattering [52] and by shell-model EFF lattice dynamics calculations [53]. The phonon spectra for the cubic polymorph c-MgH2 show a large number of imaginary frequencies for all nine different volumes. Therefore, this polymorph is not considered for the heat capacity calculations.
Figure 2.
The phonon dispersion (left) and density of states (right) computed for the polymorph α-MgH2.
4. The canonical partition function and the Helmholtz free energy
The canonical partition function of the system is the defined as ZNVT=∑ie−EiNVkBT, where the summation is done over all the states that are characterized by the energies Ei of the system formed by N particles that occupy the volume V and is kept under the temperature T. kB is the Boltzmann’s constant.
The thermodynamic parameters of the system can be defined as
U=kBT2∂lnZ∂TN,V−average potential energyE8
S=kBlnZ+U/T−entropyE9
H=U+P⋅V−enthalpyE10
F=U−T⋅S−Helmholtz free energyE11
In the relation above kB is the Boltzmann constant, T is the temperature, P is the pressure, and V is the volume of the unit cell. Enthalpy, defined as H=U+P⋅V, is a measure of a system capacity to release heat as a nonmechanical work. The most fundamental thermodynamic parameter is the Gibbs free energy, which is defined as GPT=F+p⋅V=H−T⋅S.
Based on the Helmholtz free energy, other important thermodynamic parameters can be defined:
the bulk modulus BT=V∂2F∂V2T, which describes the resistance of a material to the compression,
the isochoric heat capacity CV=−T∂2F∂T2V, which is the amount of heat per unit mass of material that is required to raise the temperature by one unit under the condition of the constant volume,
the isobaric heat capacity CP=∂H∂TP=CV−T∂V∂TP2∂P∂VT, and the volumetric thermal expansion as αV=1V∂V∂TP. Generally, the energy of the system can be decomposed based on the different degrees of freedom as the electronic and nuclear (translation, rotation, and vibration) motions, domains contributions (bulk, surface, interface, and defects), or phenomena (magnetism, irradiation). Some hybrid contributions have to be added in case of not completely separation of the different freedom degrees (as example, the electron–phonon coupling). In the case of the crystalline systems, the translation and rotation motions of the atomic basis are not present, and their contributions are not included in the structure of the Helmholtz free energy. Furthermore, the product PV is very small in comparison with the other terms, and usually it is neglected. Therefore, usually the stability of the crystals is characterized by the Helmholtz free energy, rather than the Gibbs energy.
For a nonmagnetic ideal crystal, the Helmholtz free energy can be written as:
FVT=U0V+FelVT+FphonVTE12
where the first term in Eq. (12) corresponds to the total energy, the second term is the contribution of the electronic excitation, and the last term is given by the nuclear vibrational motion. The first and third terms can be calculated both by the electronic structure or empirical force fields methods and the second one just by electronic structure methods.
The electronic structure methods typically do not take explicitly into account the temperature effects on the atomic ground state and the computed properties correspond to T = 0 K. However, for the incomplete occupied bands, like in case of the metals, the occupation probability of the electronic levels ∈ is described by the Fermi-Dirac distribution f∈T=exp∈−EFkBT+1−1, where the EF is the Fermi level, the last occupied electronic level, with the value given by the normalization condition ∫f∈Td∈=1. The energy due to the electronic excitation is UelVT=∫nV∈f∈d∈−∫nV∈∈d∈, where nV∈ is the electronic density of states computed for the volume V. The corresponding electronic entropy is SelV=−gkB∫fVTlnf(VT)+1−fVTln1−fVT.
where g is equal to 1 for collinear spin polarized or 2 for non-spin-polarized systems. The electronic Helmholtz free energy is FelVT=UelVT−TSelVT. The electronic excitation term is calculated based on the Mermin theorem [54]. Felis important for the metallic systems, especially at high temperatures. Usually it is neglected in the other cases. However, the partial occupation of the electronic level can be used also for the nonmetallic systems in the smearing scheme [55] that is useful to accelerate the self-consistent field convergence, mixing the occupied and unoccupied states that are clearly separated at T = 0 K. The contribution of the smearing to the electronic energy is refereed as Mermin free energy. The smearing scheme was applied to perform the calculations for the investigated polymorphs of the magnesium hydride. It is efficient in the accelerating the SCF convergence, inducing a very low correction to the total energies (see Table 1). The electronic contribution to the electronic Helmholtz energy is negligible except for the cubic polymorph c-MgH2, which has metallic properties.
The third term in Eq. (12) is the contribution of the phonon vibration and is dependent on temperature. The partition function corresponding to the phonon is Zvib=∏q→,j∑n=0∞e−n+12ℏωq→jkBT and the vibrational Helmholtz energy in the harmonic approximation is depending on temperature only by the phonon contribution calculated for the equilibrium volume Veq
For low temperatures, the amplitude of the vibrations is reduced and the harmonic approximation is valid for almost all the cases. For Na atoms per unit cell, the isochoric heat capacity is
5. Computational thermodynamics in quasi-harmonic approximation
The neglect of anharmonicity by the truncation of the third term in the development of the total energy leads to well-known unphysical behavior [56]: the zero thermal expansion, infinite thermal conductivity, and phonon lifetime. The inclusion of temperature effects, primarily related to the vibrational degrees of freedom inside the crystal, is more delicate. There are essentially two mainstream ways of incorporating temperature in a theoretical calculation: Molecular Dynamics [57] and Monte Carlo [58] simulations, and the quasiharmonic approximation (QHA) [59]. The former techniques are ideally suited for situations close to the classical limit, at temperatures close to or including the melting temperature. The latter is assuming the harmonic approximation at any given crystal geometry, even if it does not correspond to the equilibrium structure. Plenty of examples of the success of QHA in the prediction of thermodynamic properties and phase stability of solids can be found in the literature [60].
In QHA, the phonon calculations are done for several volumes ωq→,jV and the Helmholtz free energy becomes
where UcoldV=U0V+12∑q→,jℏωq→,jV is the cold potential energy (T = 0 K), and FthV=kBT∑q→,jlog1−exp−ℏωq→,jVkBT is the thermal component of the Helmholtz free energy given by the phonons.
The accurate calculation of the phonon frequency requires the energy evaluation by electronic structure methods, but also the usage of some empirical force fields might give good results [62]. At very low temperature, the thermal part of the phonon contribution is negligible and the entropy does not contribute to the Gibbs energy as the product TS is also negligible. In these conditions, the Gibbs energy of the crystal becomes G≅Ucold+PV. The product PV is very small comparing with the total energy and the Gibbs energy is approximated with the cold energy. The anharmonic effects become significant for the magnesium hydride just above 800 K [63]. Therefore, we do not consider here the anharmonic effects on the thermodynamic properties.
Alternatively to the static calculations of the phonons in the harmonic approximation, the anharmonic phonon spectra can be calculated by Molecular Dynamics simulations [64, 65]. The phonon dispersion of a given phonon wave vector q→ can be evaluated from MD simulations by computing the Fourier transforms of velocity–velocity correlation functions gq→ωT=∫eiωt∑I=1Naeiq→R→Iv→Itv→I0Tv→I0v→I0Tdt, where v→It is velocity of each atom I at time t, and R→I is the lattice position of the same atom. The angular brackets represent the time average for a given temperature T considered during the MD simulations. The phonon dispersions are explicitly temperature-dependent and include also the anharmonic contributions. The MD calculations fully consider the anharmonic effects, but do not consider the ZPE effects, as they follow the classical statistical mechanics [66]. Therefore, a quantum correction has to be considered, especially for low temperatures [67].
6. Computational thermodynamics
6.1 Thermodynamic modeling
Considering the temperature effects on the volume the pressure can be formulated as
PVT=−∂F∂VT=PstatV0K+PphonVT+PaeVTE17
where P0V0K is the static pressure computed by Eq. (2), PphonVT is phonon contribution to the pressure, and PaeVT is the anharmonic and electronic thermal pressure. The thermal pressure is calculated as the derivative of the thermal free energy
where γq→,j=−Vωq→,j∂lnωq→,j∂V=−V2ωq→,j2eq→,j∂Dq→∂Veq→,j is the so-called mode Grüneisen parameter, which characterizes the volume dependences of the frequency of the mode q→j. Similarly to Eq. (2), the pressure PV=−dFdVT can be calculated for each considered volume of the unit cell based on the equations of state of Murnaghan type [46]. The enthalpy can be calculated as H=U0V+PV.
6.2 Debye method
The Debye model [68] considers a simple form for the DOS of the vibration modes gω=C⋅ω2⋅Θω−ωD, where Θ is the Heaviside step function, and C=9Na/ωD3 is a constant determined from the condition C∫gωdω=3Na. Thus, the phonon modes are populated just below ωD, which is called Debye frequency. The phonon Helmholtz free energy and the isochoric heat capacity are
FphonDebyeT=NakBT9TD8T+3ln1−e−TDT−DTDTE19
where the function DTDT=3TD/T3∫0TD/Tx3ex−1dx is the Debye integral and the parameter TD=ℏkB6π2V12Na13fσBsM is the Debye Temperature, which can be interpreted as the temperature at which each mode below the highest-frequency mode ωD is excited. The Debye model allows the calculation of the thermodynamic parameters avoiding the phonon calculations if the Debye temperature can be determined from experimental or theoretical elastic constants [69] or from the value of the melting temperature [70]. The estimated Debye temperatures for T = 300 K are given in the Table 1, for all the polymorphs.
6.3 Heat capacity: Grüneisen parameter
The weighted average heat capacity of the individual phonon modes
γ=∑q→,jγq→,jCVq→j∑q→,jCVq→jE20
is the total Grüneisen parameter, where
CVq→j=kBℏωq→,jkBT2expℏωq→,jkBT−1−2expℏωq→,jkBTE21
is the contribution of each vibration mode q→j to the isochoric heat capacity
CV=∑q→,jCVq→jE22
The constant volume (isochoric) heat capacity was obtained from the quasi-harmonic phonon frequencies calculated at each fixed volume. The isochoric heat capacity at each temperature is then obtained interpolating at the temperature-dependent volume values obtained at each temperature from the minimization of the free energy.
The constant pressure (isobaric) heat capacity is obtained as
CP=CV+TVβ2BTE23
where BTVT=1V∂2FVT∂V2T is the isothermal bulk modulus, which can be calculated as a function of temperature [61].
In Figure 3, the predicted isochoric and isobaric heat capacities of the magnesium hydride polymorphs are shown to have similar behavior, with deviations at 800 K below 3.81 and 3.44 J mol−1 K−1, respectively. The isochoric and isobaric heat capacities have the same values bellow 400 K. The predicted heat capacities for the polymorph α-MgH2 are in excellent agreement with the experimental data [52, 71, 72] despite that the calculations are done for ideal crystalline systems, real sample are generally polycrystalline and contain a lot of defects depending on the preparation procedure. The iso- and anisotropic calculated isochoric heat capacities for α-MgH2 are identical while those for the isobaric heat capacity are almost identical up to 550 K, which is the decomposition temperature of the crystal; even at the higher temperatures, the iso- and aniso- differences are marginal. Similar results regarding the isotropic heat capacities are obtained for the other non-cubic polymorphs. Therefore, we conclude that the isotropic treatment by uniform contraction/expansion of the unit cell of the considered magnesium hydride polymorphs introduces negligible effects on the calculated isochoric heat capacities, below their decomposition temperatures. The electronic contribution to the heat capacity was found to be negligible.
Figure 3.
The isochoric (left) and the isobaric (right) heat capacities versus temperature, computed for the five polymorphs of the magnesium hydride α, β, δ, ε, and γ by the isotropic procedure. In addition, the Cv versus T obtained by the anisotropic procedure is presented for α-MgH2 (red open circle). The experimental data available for α-MgH2 are indicated by full symbols.
The heat capacity in the Debye model is CVDebye=3NakB4DTDT−3TD/TeTD/T−1. The formula is valid at low temperatures, predicting correctly the temperature dependence of the heat capacity as being proportional to the temperature at power 3, and recovers at high temperatures the Dulong–Petit law, which states that the heat capacity is proportional with the number of atoms per unit cell 3NakB at high temperatures.
The Molecular Dynamics and Monte Carlo simulations in tandem with the thermodynamic integration [73] and free energy perturbation [74] methods can be used to calculate the Helmholtz free energy and other thermodynamic properties. The electronic structure methods or well-parameterized EFF can be used in MD simulations to the vibration DOS and to calculate the thermodynamic properties such as heat capacity [75]. The heat capacity can be directly evaluated in MD or MC simulations as CV/P=E2−E2kBT2, where E is total energy calculated at each simulation step, and the brackets indicate the average over the sequence of configurations produced during the MD or MC steps. Depending on the used thermodynamic ensemble, canonic (Na, V, T constant) or the isothermal-isobaric (Na, P, T constant), the isochoric Cv, and isobaric Cp heat capacity, respectively, are calculated. The MD and MC simulations involve the evaluation of the energy and interatomic forces for a very large number of atomic configurations and are not practical to involve electronic structure methods, especially in the case of large systems.
7. Conclusions
The electronic structure and empirical force fields methods are discussed shortly, emphasizing the calculation of the total energy and its derivatives, as well as the phonon spectra. The methods for the calculation of the Helmholtz, Enthalpy, and Gibbs energy are described. The heat capacities of several polymorphs of the magnesium hydride are investigated by density functional theory within the frame of the quasi-harmonic approximation. The predicted temperature variation of the heat capacity for the polymorph of the magnesium hydride α-MgH2 is in good agreement with the experimental data. We assess the heat capacity for several other polymorphs of MgH2, for which there is no available experimental or theoretical information.
Acknowledgments
The work was supported by a grant of the Romanian Ministry of Education and Research, CCCDI – UEFISCDI, project number PN-III-P2-2.1-PED-2019-4816, within PNCDI III. CV and AV acknowledge the financial support for mutual visits provided on the basis of the inter-academic exchange agreement between the Bulgarian Academy of Science and the Romanian Academy.
Conflict of interest
The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
\n',keywords:"density functional theory, phonons, thermodynamic calculations, Gibbs free energy, heat capacity, magnesium hydrides",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/81365.pdf",chapterXML:"https://mts.intechopen.com/source/xml/81365.xml",downloadPdfUrl:"/chapter/pdf-download/81365",previewPdfUrl:"/chapter/pdf-preview/81365",totalDownloads:22,totalViews:0,totalCrossrefCites:0,dateSubmitted:"December 22nd 2021",dateReviewed:"February 28th 2022",datePrePublished:"April 18th 2022",datePublished:"June 23rd 2022",dateFinished:"April 18th 2022",readingETA:"0",abstract:"The theoretical aspects of the thermodynamic calculation of the Gibbs energy and heat capacity of a crystalline system within the frame of the Density Functional Theory (DFT) are introduced in the present chapter. Various approximations of phonon motion (harmonic, quasiharmonic, and anharmonic) and their effects on the thermodynamic properties are discussed. The theoretical basis of the thermodynamic approach of the heat capacity of crystals for given thermodynamic conditions is presented, having as example six polymorphs of the magnesium hydrides.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/81365",risUrl:"/chapter/ris/81365",signatures:"Viorel Chihaia, Valentin Alexiev and Hasan S. AlMatrouk",book:{id:"10696",type:"book",title:"Applications of Calorimetry",subtitle:null,fullTitle:"Applications of Calorimetry",slug:"applications-of-calorimetry",publishedDate:"June 23rd 2022",bookSignature:"José Luis Rivera Armenta and Cynthia Graciela Flores Hernández",coverURL:"https://cdn.intechopen.com/books/images_new/10696.jpg",licenceType:"CC BY 3.0",editedByType:"Edited by",isbn:"978-1-80355-322-1",printIsbn:"978-1-80355-321-4",pdfIsbn:"978-1-80355-323-8",isAvailableForWebshopOrdering:!0,editors:[{id:"107855",title:"Dr.",name:"Jose Luis",middleName:null,surname:"Rivera Armenta",slug:"jose-luis-rivera-armenta",fullName:"Jose Luis Rivera Armenta"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}},authors:[{id:"289039",title:"Dr.",name:"Viorel",middleName:null,surname:"Chihaia",fullName:"Viorel Chihaia",slug:"viorel-chihaia",email:"vchihaia@icf.ro",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",institution:null},{id:"437996",title:"Prof.",name:"Valentin",middleName:null,surname:"Alexiev",fullName:"Valentin Alexiev",slug:"valentin-alexiev",email:"valex000@gmail.com",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",institution:null},{id:"437997",title:"Dr.",name:"Hasan S.",middleName:null,surname:"AlMatrouk",fullName:"Hasan S. AlMatrouk",slug:"hasan-s.-almatrouk",email:"hasan.almatrouk@gmail.com",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",institution:{name:"Kuwait Institute for Scientific Research",institutionURL:null,country:{name:"Kuwait"}}}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Total energy computation methods",level:"1"},{id:"sec_2_2",title:"2.1 The simulation methods for the electronic ground states",level:"2"},{id:"sec_3_2",title:"2.2 The simulation methods for the electronic excited states",level:"2"},{id:"sec_4_2",title:"2.3 Static and dynamic properties",level:"2"},{id:"sec_5_2",title:"2.4 Equation of states and pressure",level:"2"},{id:"sec_7",title:"3. Phonon calculations in lattice dynamics method: Harmonic approximation",level:"1"},{id:"sec_8",title:"4. The canonical partition function and the Helmholtz free energy",level:"1"},{id:"sec_9",title:"5. Computational thermodynamics in quasi-harmonic approximation",level:"1"},{id:"sec_10",title:"6. Computational thermodynamics",level:"1"},{id:"sec_10_2",title:"6.1 Thermodynamic modeling",level:"2"},{id:"sec_11_2",title:"6.2 Debye method",level:"2"},{id:"sec_12_2",title:"6.3 Heat capacity: Grüneisen parameter",level:"2"},{id:"sec_14",title:"7. Conclusions",level:"1"},{id:"sec_15",title:"Acknowledgments",level:"1"},{id:"sec_18",title:"Conflict of interest",level:"1"}],chapterReferences:[{id:"B1",body:'AlMatrouk HS, Chihaia V, Alexiev V. Density functional study of the thermodynamic properties and phase diagram of the magnesium hydride. Calphad. 2018;60:7-15. DOI: 10.1016/j.calphad.2017.11.001'},{id:"B2",body:'Vajeeston P, Ravindran P, Hauback BC, Fjellvåg H, Kjekshus A, Furuseth S, et al. Structural stability and pressure-induced phase transitions in MgH2. Physical Review B. 2006;73:224102-224108. DOI: 10.1103/PhysRevB.73.224102'},{id:"B3",body:'Yartys VA et al. 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Thermochemical Tables. Last Update to Data Content. College Park, Maryland, United States Available from: https://janaf.nist.gov: American Institute of Physics; 1998 [Accessed on 21 November, 2021]'},{id:"B73",body:'Barril X, Orozco M, Luque FJ. Predicting relative binding free energies of tacrine-Huperzine a hybrids as inhibitors of acetylcholinesterase. Journal of Medicinal Chemistry. 1999;42:5110-5119. DOI: 10.1021/jm990371u'},{id:"B74",body:'Frenkel D, Smit B. Understanding Molecular Simulation: From Algorithms to Applications. Cambridge, Massachusetts, United States: Academic Press; 2002. DOI: 10.1016/B978-0-12-267351-1.X5000-7 ISBN: 978-0-12-267351-1'},{id:"B75",body:'Gowdini E, Ahmad AA, Mabudi A, Hadipour NL, Kharazian B. A molecular dynamics study on the thermal properties of carbon-based gold nanoparticles. The Journal of Molecular Modeling. 2020;26:307-309. 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Copyright is the term used to describe the rights related to the publication and distribution of original Works. Most importantly from a publisher's perspective, copyright governs how Authors, publishers and the general public can use, publish, and distribute publications.
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IntechOpen only publishes manuscripts for which it has publishing rights. This is governed by a publication agreement between the Author and IntechOpen. This agreement is accepted by the Author when the manuscript is submitted and deals with both the rights of the publisher and Author, as well as any obligations concerning a particular manuscript. However, in accepting this agreement, Authors continue to retain significant rights to use and share their publications.
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By accepting the agreement terms Authors retain their copyright on their Work but grant broad publishing and distribution rights to the publisher.
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Depending on the type of publication (Chapter or Long Form Monograph/Compacts; see definitions below), IntechOpen applies a Creative Commons license to the publication, allowing readers to use and share it freely.
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Agreement samples are listed here for the convenience of prospective Authors:
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An analysis of regime shift index reveals that the worldwide TC activity experienced four significant abrupt changes during 1960–2014, including (i) an abrupt increase/decrease in the eastern North Pacific (ENP)/western North Pacific (WNP) in the early 1970s, (ii) an abrupt increase in the ENP and WNP in the early 1980s, (iii) an abrupt increase in the North Atlantic and ENP in the middle 1990s, and (iv) an abrupt decrease in the WNP and western South Pacific in the late 1990s. Three of them are identified concurrent with a significant CRS. The possible influence of a CRS on the abrupt change of TC activity in various genesis regions is addressed. We demonstrate that a CRS induced time mean state shift results in a rapid change in the large-scale dynamic and thermodynamic conditions, which substantially contributes to the abrupt change of TC activity in various genesis regions. 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He also obtained an MSc in Molecular and Genetic Medicine, and a Ph.D. in Clinical Immunology and Human Genetics from the University of Sheffield, UK. He also completed a short-term fellowship in Pediatric Clinical Immunology and Bone Marrow Transplantation at Newcastle General Hospital, England. Dr. Rezaei is a Full Professor of Immunology and Vice Dean of International Affairs and Research, at the School of Medicine, Tehran University of Medical Sciences, and the co-founder and head of the Research Center for Immunodeficiencies. He is also the founding president of the Universal Scientific Education and Research Network (USERN). Dr. Rezaei has directed more than 100 research projects and has designed and participated in several international collaborative projects. He is an editor, editorial assistant, or editorial board member of more than forty international journals. He has edited more than 50 international books, presented more than 500 lectures/posters in congresses/meetings, and published more than 1,100 scientific papers in international journals.",institutionString:"Tehran University of Medical Sciences",institution:{name:"Tehran University of Medical Sciences",country:{name:"Iran"}}},{id:"180733",title:"Dr.",name:"Jean",middleName:null,surname:"Engohang-Ndong",slug:"jean-engohang-ndong",fullName:"Jean Engohang-Ndong",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/180733/images/system/180733.png",biography:"Dr. Jean Engohang-Ndong was born and raised in Gabon. After obtaining his Associate Degree of Science at the University of Science and Technology of Masuku, Gabon, he continued his education in France where he obtained his BS, MS, and Ph.D. in Medical Microbiology. He worked as a post-doctoral fellow at the Public Health Research Institute (PHRI), Newark, NJ for four years before accepting a three-year faculty position at Brigham Young University-Hawaii. Dr. Engohang-Ndong is a tenured faculty member with the academic rank of Full Professor at Kent State University, Ohio, where he teaches a wide range of biological science courses and pursues his research in medical and environmental microbiology. Recently, he expanded his research interest to epidemiology and biostatistics of chronic diseases in Gabon.",institutionString:"Kent State University",institution:{name:"Kent State University",country:{name:"United States of America"}}},{id:"188773",title:"Prof.",name:"Emmanuel",middleName:null,surname:"Drouet",slug:"emmanuel-drouet",fullName:"Emmanuel Drouet",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/188773/images/system/188773.png",biography:"Emmanuel Drouet, PharmD, is a Professor of Virology at the Faculty of Pharmacy, the University Grenoble-Alpes, France. As a head scientist at the Institute of Structural Biology in Grenoble, Dr. Drouet’s research investigates persisting viruses in humans (RNA and DNA viruses) and the balance with our host immune system. He focuses on these viruses’ effects on humans (both their impact on pathology and their symbiotic relationships in humans). He has an excellent track record in the herpesvirus field, and his group is engaged in clinical research in the field of Epstein-Barr virus diseases. He is the editor of the online Encyclopedia of Environment and he coordinates the Universal Health Coverage education program for the BioHealth Computing Schools of the European Institute of Science.",institutionString:null,institution:{name:"Grenoble Alpes University",country:{name:"France"}}},{id:"131400",title:"Prof.",name:"Alfonso J.",middleName:null,surname:"Rodriguez-Morales",slug:"alfonso-j.-rodriguez-morales",fullName:"Alfonso J. Rodriguez-Morales",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/131400/images/system/131400.png",biography:"Dr. Rodriguez-Morales is an expert in tropical and emerging diseases, particularly zoonotic and vector-borne diseases (especially arboviral diseases). He is the president of the Travel Medicine Committee of the Pan-American Infectious Diseases Association (API), as well as the president of the Colombian Association of Infectious Diseases (ACIN). He is a member of the Committee on Tropical Medicine, Zoonoses, and Travel Medicine of ACIN. He is a vice-president of the Latin American Society for Travel Medicine (SLAMVI) and a Member of the Council of the International Society for Infectious Diseases (ISID). Since 2014, he has been recognized as a Senior Researcher, at the Ministry of Science of Colombia. He is a professor at the Faculty of Medicine of the Fundacion Universitaria Autonoma de las Americas, in Pereira, Risaralda, Colombia. He is an External Professor, Master in Research on Tropical Medicine and International Health, Universitat de Barcelona, Spain. He is also a professor at the Master in Clinical Epidemiology and Biostatistics, Universidad Científica del Sur, Lima, Peru. In 2021 he has been awarded the “Raul Isturiz Award” Medal of the API. Also, in 2021, he was awarded with the “Jose Felix Patiño” Asclepius Staff Medal of the Colombian Medical College, due to his scientific contributions to COVID-19 during the pandemic. He is currently the Editor in Chief of the journal Travel Medicine and Infectious Diseases. His Scopus H index is 47 (Google Scholar H index, 68).",institutionString:"Institución Universitaria Visión de las Américas, Colombia",institution:null},{id:"332819",title:"Dr.",name:"Chukwudi Michael",middleName:"Michael",surname:"Egbuche",slug:"chukwudi-michael-egbuche",fullName:"Chukwudi Michael Egbuche",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/332819/images/14624_n.jpg",biography:"I an Dr. Chukwudi Michael Egbuche. I am a Senior Lecturer in the Department of Parasitology and Entomology, Nnamdi Azikiwe University, Awka.",institutionString:null,institution:{name:"Nnamdi Azikiwe University",country:{name:"Nigeria"}}},{id:"284232",title:"Mr.",name:"Nikunj",middleName:"U",surname:"Tandel",slug:"nikunj-tandel",fullName:"Nikunj Tandel",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/284232/images/8275_n.jpg",biography:'Mr. Nikunj Tandel has completed his Master\'s degree in Biotechnology from VIT University, India in the year of 2012. He is having 8 years of research experience especially in the field of malaria epidemiology, immunology, and nanoparticle-based drug delivery system against the infectious diseases, autoimmune disorders and cancer. He has worked for the NIH funded-International Center of Excellence in Malaria Research project "Center for the study of complex malaria in India (CSCMi)" in collaboration with New York University. The preliminary objectives of the study are to understand and develop the evidence-based tools and interventions for the control and prevention of malaria in different sites of the INDIA. Alongside, with the help of next-generation genomics study, the team has studied the antimalarial drug resistance in India. Further, he has extended his research in the development of Humanized mice for the study of liver-stage malaria and identification of molecular marker(s) for the Artemisinin resistance. At present, his research focuses on understanding the role of B cells in the activation of CD8+ T cells in malaria. Received the CSIR-SRF (Senior Research Fellow) award-2018, FIMSA (Federation of Immunological Societies of Asia-Oceania) Travel Bursary award to attend the IUIS-IIS-FIMSA Immunology course-2019',institutionString:"Nirma University",institution:{name:"Nirma University",country:{name:"India"}}},{id:"334383",title:"Ph.D.",name:"Simone",middleName:"Ulrich",surname:"Ulrich Picoli",slug:"simone-ulrich-picoli",fullName:"Simone Ulrich Picoli",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/334383/images/15919_n.jpg",biography:"Graduated in Pharmacy from Universidade Luterana do Brasil (1999), Master in Agricultural and Environmental Microbiology from Federal University of Rio Grande do Sul (2002), Specialization in Clinical Microbiology from Universidade de São Paulo, USP (2007) and PhD in Sciences in Gastroenterology and Hepatology (2012). She is currently an Adjunct Professor at Feevale University in Medicine and Biomedicine courses and a permanent professor of the Academic Master\\'s Degree in Virology. She has experience in the field of Microbiology, with an emphasis on Bacteriology, working mainly on the following topics: bacteriophages, bacterial resistance, clinical microbiology and food microbiology.",institutionString:null,institution:{name:"Universidade Feevale",country:{name:"Brazil"}}},{id:"229220",title:"Dr.",name:"Amjad",middleName:"Islam",surname:"Aqib",slug:"amjad-aqib",fullName:"Amjad Aqib",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/229220/images/system/229220.png",biography:"Dr. Amjad Islam Aqib obtained a DVM and MSc (Hons) from University of Agriculture Faisalabad (UAF), Pakistan, and a PhD from the University of Veterinary and Animal Sciences Lahore, Pakistan. Dr. Aqib joined the Department of Clinical Medicine and Surgery at UAF for one year as an assistant professor where he developed a research laboratory designated for pathogenic bacteria. Since 2018, he has been Assistant Professor/Officer in-charge, Department of Medicine, Manager Research Operations and Development-ORIC, and President One Health Club at Cholistan University of Veterinary and Animal Sciences, Bahawalpur, Pakistan. He has nearly 100 publications to his credit. His research interests include epidemiological patterns and molecular analysis of antimicrobial resistance and modulation and vaccine development against animal pathogens of public health concern.",institutionString:"Cholistan University of Veterinary and Animal Sciences",institution:null},{id:"62900",title:"Prof.",name:"Fethi",middleName:null,surname:"Derbel",slug:"fethi-derbel",fullName:"Fethi Derbel",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/62900/images/system/62900.jpeg",biography:"Professor Fethi Derbel was born in 1960 in Tunisia. He received his medical degree from the Sousse Faculty of Medicine at Sousse, University of Sousse, Tunisia. He completed his surgical residency in General Surgery at the University Hospital Farhat Hached of Sousse and was a member of the Unit of Liver Transplantation in the University of Rennes, France. He then worked in the Department of Surgery at the Sahloul University Hospital in Sousse. Professor Derbel is presently working at the Clinique les Oliviers, Sousse, Tunisia. His hospital activities are mostly concerned with laparoscopic, colorectal, pancreatic, hepatobiliary, and gastric surgery. He is also very interested in hernia surgery and performs ventral hernia repairs and inguinal hernia repairs. He has been a member of the GREPA and Tunisian Hernia Society (THS). During his residency, he managed patients suffering from diabetic foot, and he was very interested in this pathology. For this reason, he decided to coordinate a book project dealing with the diabetic foot. Professor Derbel has published many articles in journals and collaborates intensively with IntechOpen Access Publisher as an editor.",institutionString:"Clinique les Oliviers",institution:null},{id:"300144",title:"Dr.",name:"Meriem",middleName:null,surname:"Braiki",slug:"meriem-braiki",fullName:"Meriem Braiki",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/300144/images/system/300144.jpg",biography:"Dr. Meriem Braiki is a specialist in pediatric surgeon from Tunisia. She was born in 1985. She received her medical degree from the University of Medicine at Sousse, Tunisia. She achieved her surgical residency training periods in Pediatric Surgery departments at University Hospitals in Monastir, Tunis and France.\r\nShe is currently working at the Pediatric surgery department, Sidi Bouzid Hospital, Tunisia. Her hospital activities are mostly concerned with laparoscopic, parietal, urological and digestive surgery. She has published several articles in diffrent journals.",institutionString:"Sidi Bouzid Regional Hospital",institution:null},{id:"229481",title:"Dr.",name:"Erika M.",middleName:"Martins",surname:"de Carvalho",slug:"erika-m.-de-carvalho",fullName:"Erika M. de Carvalho",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/229481/images/6397_n.jpg",biography:null,institutionString:null,institution:{name:"Oswaldo Cruz Foundation",country:{name:"Brazil"}}},{id:"186537",title:"Prof.",name:"Tonay",middleName:null,surname:"Inceboz",slug:"tonay-inceboz",fullName:"Tonay Inceboz",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/186537/images/system/186537.jfif",biography:"I was graduated from Ege University of Medical Faculty (Turkey) in 1988 and completed his Med. PhD degree in Medical Parasitology at the same university. I became an Associate Professor in 2008 and Professor in 2014. I am currently working as a Professor at the Department of Medical Parasitology at Dokuz Eylul University, Izmir, Turkey.\n\nI have given many lectures, presentations in different academic meetings. I have more than 60 articles in peer-reviewed journals, 18 book chapters, 1 book editorship.\n\nMy research interests are Echinococcus granulosus, Echinococcus multilocularis (diagnosis, life cycle, in vitro and in vivo cultivation), and Trichomonas vaginalis (diagnosis, PCR, and in vitro cultivation).",institutionString:"Dokuz Eylül University",institution:{name:"Dokuz Eylül University",country:{name:"Turkey"}}},{id:"71812",title:"Prof.",name:"Hanem Fathy",middleName:"Fathy",surname:"Khater",slug:"hanem-fathy-khater",fullName:"Hanem Fathy Khater",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/71812/images/1167_n.jpg",biography:"Prof. Khater is a Professor of Parasitology at Benha University, Egypt. She studied for her doctoral degree, at the Department of Entomology, College of Agriculture, Food and Natural Resources, University of Missouri, Columbia, USA. She has completed her Ph.D. degrees in Parasitology in Egypt, from where she got the award for “the best scientific Ph.D. dissertation”. She worked at the School of Biological Sciences, Bristol, England, the UK in controlling insects of medical and veterinary importance as a grant from Newton Mosharafa, the British Council. Her research is focused on searching of pesticides against mosquitoes, house flies, lice, green bottle fly, camel nasal botfly, soft and hard ticks, mites, and the diamondback moth as well as control of several parasites using safe and natural materials to avoid drug resistances and environmental contamination.",institutionString:null,institution:{name:"Banha University",country:{name:"Egypt"}}},{id:"99780",title:"Prof.",name:"Omolade",middleName:"Olayinka",surname:"Okwa",slug:"omolade-okwa",fullName:"Omolade Okwa",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/99780/images/system/99780.jpg",biography:"Omolade Olayinka Okwa is presently a Professor of Parasitology at Lagos State University, Nigeria. She has a PhD in Parasitology (1997), an MSc in Cellular Parasitology (1992), and a BSc (Hons) Zoology (1990) all from the University of Ibadan, Nigeria. She teaches parasitology at the undergraduate and postgraduate levels. She was a recipient of a Commonwealth fellowship supported by British Council tenable at the Centre for Entomology and Parasitology (CAEP), Keele University, United Kingdom between 2004 and 2005. She was awarded an Honorary Visiting Research Fellow at the same university from 2005 to 2007. \nShe has been an external examiner to the Department of Veterinary Microbiology and Parasitology, University of Ibadan, MSc programme between 2010 and 2012. She is a member of the Nigerian Society of Experimental Biology (NISEB), Parasitology and Public Health Society of Nigeria (PPSN), Science Association of Nigeria (SAN), Zoological Society of Nigeria (ZSN), and is Vice Chairperson of the Organisation of Women in Science (OWSG), LASU chapter. She served as Head of Department of Zoology and Environmental Biology, Lagos State University from 2007 to 2010 and 2014 to 2016. She is a reviewer for several local and international journals such as Unilag Journal of Science, Libyan Journal of Medicine, Journal of Medicine and Medical Sciences, and Annual Research and Review in Science. \nShe has authored 45 scientific research publications in local and international journals, 8 scientific reviews, 4 books, and 3 book chapters, which includes the books “Malaria Parasites” and “Malaria” which are IntechOpen access publications.",institutionString:"Lagos State University",institution:{name:"Lagos State University",country:{name:"Nigeria"}}},{id:"273100",title:"Dr.",name:"Vijay",middleName:null,surname:"Gayam",slug:"vijay-gayam",fullName:"Vijay Gayam",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/273100/images/system/273100.jpeg",biography:"Dr. Vijay Bhaskar Reddy Gayam is currently practicing as an internist at Interfaith Medical Center in Brooklyn, New York, USA. 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\r\n\tIn general, the harsher the environmental conditions in an ecosystem, the lower the biodiversity. Changes in the environment caused by human activity accelerate the impoverishment of biodiversity.
\r\n
\r\n\tBiodiversity refers to “the variability of living organisms from any source, including terrestrial, marine and other aquatic ecosystems and the ecological complexes of which they are part; it includes diversity within each species, between species, and that of ecosystems”.
\r\n
\r\n\tBiodiversity provides food security and constitutes a gene pool for biotechnology, especially in the field of agriculture and medicine, and promotes the development of ecotourism.
\r\n
\r\n\tCurrently, biologists admit that we are witnessing the first phases of the seventh mass extinction caused by human intervention. It is estimated that the current rate of extinction is between a hundred and a thousand times faster than it was when man first appeared. The disappearance of species is caused not only by an accelerated rate of extinction, but also by a decrease in the rate of emergence of new species as human activities degrade the natural environment. The conservation of biological diversity is "a common concern of humanity" and an integral part of the development process. Its objectives are “the conservation of biological diversity, the sustainable use of its components, and the fair and equitable sharing of the benefits resulting from the use of genetic resources”.
\r\n
\r\n\tThe following are the main causes of biodiversity loss:
\r\n
\r\n\t• The destruction of natural habitats to expand urban and agricultural areas and to obtain timber, minerals and other natural resources.
\r\n
\r\n\t• The introduction of alien species into a habitat, whether intentionally or unintentionally which has an impact on the fauna and flora of the area, and as a result, they are reduced or become extinct.
\r\n
\r\n\t• Pollution from industrial and agricultural products, which devastate the fauna and flora, especially those in fresh water.
\r\n
\r\n\t• Global warming, which is seen as a threat to biological diversity, and will become increasingly important in the future.
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\r\n\tThe environment is subject to severe anthropic effects. Among them are those associated with pollution, resource extraction and overexploitation, loss of biodiversity, soil degradation, disorderly land occupation and planning, and many others. These anthropic effects could potentially be caused by any inadequate management of the environment. However, ecosystems have a resilience that makes them react to disturbances which mitigate the negative effects. It is critical to understand how ecosystems, natural and anthropized, including urban environments, respond to actions that have a negative influence and how they are managed. It is also important to establish when the limits marked by the resilience and the breaking point are achieved and when no return is possible. The main focus for the chapters is to cover the subjects such as understanding how the environment resilience works, the mechanisms involved, and how to manage them in order to improve our interactions with the environment and promote the use of adequate management practices such as those outlined in the United Nations’ Sustainable Development Goals.
\r\n\tPollution is caused by a wide variety of human activities and occurs in diverse forms, for example biological, chemical, et cetera. In recent years, significant efforts have been made to ensure that the environment is clean, that rigorous rules are implemented, and old laws are updated to reduce the risks towards humans and ecosystems. However, rapid industrialization and the need for more cultivable sources or habitable lands, for an increasing population, as well as fewer alternatives for waste disposal, make the pollution control tasks more challenging. Therefore, this topic will focus on assessing and managing environmental pollution. It will cover various subjects, including risk assessment due to the pollution of ecosystems, transport and fate of pollutants, restoration or remediation of polluted matrices, and efforts towards sustainable solutions to minimize environmental pollution.
\r\n\tWater is not only a crucial substance needed for biological life on Earth, but it is also a basic requirement for the existence and development of the human society. Owing to the importance of water to life on Earth, early researchers conducted numerous studies and analyses on the liquid form of water from the perspectives of chemistry, physics, earth science, and biology, and concluded that Earth is a "water polo". Water covers approximately 71% of Earth's surface. However, 97.2% of this water is seawater, 21.5% is icebergs and glaciers, and only 0.65% is freshwater that can be used directly by humans. As a result, the amount of water reserves available for human consumption is limited. The development, utilization, and protection of freshwater resources has become the focus of water science research for the continued improvement of human livelihoods and society.
\r\n
\r\n\tWater exists as solid, liquid, and gas within Earth’s atmosphere, lithosphere, and biosphere. Liquid water is used for a variety of purposes besides drinking, including power generation, ecology, landscaping, and shipping. Because water is involved in various environmental hydrological processes as well as numerous aspects of the economy and human society, the study of various phenomena in the hydrosphere, the laws governing their occurrence and development, the relationship between the hydrosphere and other spheres of Earth, and the relationship between water and social development, are all part of water science. Knowledge systems for water science are improving continuously. Water science has become a specialized field concerned with the identification of its physical, chemical, and biological properties. In addition, it reveals the laws of water distribution, movement, and circulation, and proposes methods and tools for water development, utilization, planning, management, and protection. Currently, the field of water science covers research related to topics such as hydrology, water resources and water environment. It also includes research on water related issues such as safety, engineering, economy, law, culture, information, and education.
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Biochemistry also studies small signaling molecules, coenzymes, inhibitors, vitamins, and hormones, which play roles in life processes. Biochemical experimentation, besides coopting classical chemistry methods, e.g., chromatography, adopted new techniques, e.g., X-ray diffraction, electron microscopy, NMR, radioisotopes, and developed sophisticated microbial genetic tools, e.g., auxotroph mutants and their revertants, fermentation, etc. More recently, biochemistry embraced the ‘big data’ omics systems. Initial biochemical studies have been exclusively analytic: dissecting, purifying, and examining individual components of a biological system; in the apt words of Efraim Racker (1913 –1991), “Don’t waste clean thinking on dirty enzymes.” Today, however, biochemistry is becoming more agglomerative and comprehensive, setting out to integrate and describe entirely particular biological systems. 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We encourage the submission of manuscripts that provide novel and mechanistic insights that report significant advances in the fields. 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In recent years, the application of chemistry to biological molecules has gained significant interest in medicinal and pharmacological studies. This topic will be devoted to understanding the interplay between biomolecules and chemical compounds, their structure and function, and their potential applications in related fields. Being a part of the biochemistry discipline, the ideas and concepts that have emerged from Chemical Biology have affected other related areas. This topic will closely deal with all emerging trends in this discipline.",annualVolume:11411,isOpenForSubmission:!0,coverUrl:"https://cdn.intechopen.com/series_topics/covers/15.jpg",editor:{id:"441442",title:"Dr.",name:"Şükrü",middleName:null,surname:"Beydemir",fullName:"Şükrü Beydemir",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0033Y00003GsUoIQAV/Profile_Picture_1634557147521",institutionString:null,institution:{name:"Anadolu University",institutionURL:null,country:{name:"Turkey"}}},editorTwo:{id:"13652",title:"Prof.",name:"Deniz",middleName:null,surname:"Ekinci",fullName:"Deniz Ekinci",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002aYLT1QAO/Profile_Picture_1634557223079",institutionString:null,institution:{name:"Ondokuz Mayıs University",institutionURL:null,country:{name:"Turkey"}}},editorThree:null,editorialBoard:[{id:"241413",title:"Dr.",name:"Azhar",middleName:null,surname:"Rasul",fullName:"Azhar Rasul",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bRT1oQAG/Profile_Picture_1635251978933",institutionString:null,institution:{name:"Government College University, Faisalabad",institutionURL:null,country:{name:"Pakistan"}}},{id:"178316",title:"Ph.D.",name:"Sergey",middleName:null,surname:"Sedykh",fullName:"Sergey Sedykh",profilePictureURL:"https://mts.intechopen.com/storage/users/178316/images/system/178316.jfif",institutionString:null,institution:{name:"Novosibirsk State University",institutionURL:null,country:{name:"Russia"}}}]},{id:"17",title:"Metabolism",keywords:"Biomolecules Metabolism, Energy Metabolism, Metabolic Pathways, Key Metabolic Enzymes, Metabolic Adaptation",scope:"Metabolism is frequently defined in biochemistry textbooks as the overall process that allows living systems to acquire and use the free energy they need for their vital functions or the chemical processes that occur within a living organism to maintain life. Behind these definitions are hidden all the aspects of normal and pathological functioning of all processes that the topic ‘Metabolism’ will cover within the Biochemistry Series. 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Thus proteomics, an area of research that detects all protein forms expressed in an organism, including splice isoforms and post-translational modifications, is more suitable than genomics for a comprehensive understanding of the biochemical processes that govern life. The most common proteomics applications are currently in the clinical field for the identification, in a variety of biological matrices, of biomarkers for diagnosis and therapeutic intervention of disorders. From the comparison of proteomic profiles of control and disease or different physiological states, which may emerge, changes in protein expression can provide new insights into the roles played by some proteins in human pathologies. Understanding how proteins function and interact with each other is another goal of proteomics that makes this approach even more intriguing. Specialized technology and expertise are required to assess the proteome of any biological sample. Currently, proteomics relies mainly on mass spectrometry (MS) combined with electrophoretic (1 or 2-DE-MS) and/or chromatographic techniques (LC-MS/MS). MS is an excellent tool that has gained popularity in proteomics because of its ability to gather a complex body of information such as cataloging protein expression, identifying protein modification sites, and defining protein interactions. 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