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IntechOpen Book Series will also publish a program of research-driven Thematic Edited Volumes that focus on specific areas and allow for a more in-depth overview of a particular subject.
\\n\\nIntechOpen Book Series will be launching regularly to offer our authors and editors exciting opportunities to publish their research Open Access. We will begin by relaunching some of our existing Book Series in this innovative book format, and will expand in 2022 into rapidly growing research fields that are driving and advancing society.
\\n\\nLaunching 2021
\\n\\nArtificial Intelligence, ISSN 2633-1403
\\n\\nVeterinary Medicine and Science, ISSN 2632-0517
\\n\\nBiochemistry, ISSN 2632-0983
\\n\\nBiomedical Engineering, ISSN 2631-5343
\\n\\nInfectious Diseases, ISSN 2631-6188
\\n\\nPhysiology (Coming Soon)
\\n\\nDentistry (Coming Soon)
\\n\\nWe invite you to explore our IntechOpen Book Series, find the right publishing program for you and reach your desired audience in record time.
\\n\\nNote: Edited in October 2021
\\n"}]',published:!0,mainMedia:{caption:"",originalUrl:"/media/original/132"}},components:[{type:"htmlEditorComponent",content:'With the desire to make book publishing more relevant for the digital age and offer innovative Open Access publishing options, we are thrilled to announce the launch of our new publishing format: IntechOpen Book Series.
\n\nDesigned to cover fast-moving research fields in rapidly expanding areas, our Book Series feature a Topic structure allowing us to present the most relevant sub-disciplines. Book Series are headed by Series Editors, and a team of Topic Editors supported by international Editorial Board members. Topics are always open for submissions, with an Annual Volume published each calendar year.
\n\nAfter a robust peer-review process, accepted works are published quickly, thanks to Online First, ensuring research is made available to the scientific community without delay.
\n\nOur innovative Book Series format brings you:
\n\nIntechOpen Book Series will also publish a program of research-driven Thematic Edited Volumes that focus on specific areas and allow for a more in-depth overview of a particular subject.
\n\nIntechOpen Book Series will be launching regularly to offer our authors and editors exciting opportunities to publish their research Open Access. We will begin by relaunching some of our existing Book Series in this innovative book format, and will expand in 2022 into rapidly growing research fields that are driving and advancing society.
\n\nLaunching 2021
\n\nArtificial Intelligence, ISSN 2633-1403
\n\nVeterinary Medicine and Science, ISSN 2632-0517
\n\nBiochemistry, ISSN 2632-0983
\n\nBiomedical Engineering, ISSN 2631-5343
\n\nInfectious Diseases, ISSN 2631-6188
\n\nPhysiology (Coming Soon)
\n\nDentistry (Coming Soon)
\n\nWe invite you to explore our IntechOpen Book Series, find the right publishing program for you and reach your desired audience in record time.
\n\nNote: Edited in October 2021
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Therefore, to achieve the best effects, emphasis should be placed on optimizing and standardizing acupuncture parameters and procedures.
\r\n\r\n\tThis book intends to provide the reader with a comprehensive overview of the recent advances, new perspectives, and applications of acupuncture and moxibustion that focuses on the most important evidence-based developments in this critically important area.
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He is a senior member of the International Association for the Study of Pain, and holder of a patent for needle improvement with a supercritical fluid-treated needle.",coeditorOneBiosketch:"A pioneering researcher in acupuncture, Dr. Sun has throughout his career been appointed Dean of College of Chinese Medicine in CMU, Chinese Medicine vice Superintendent in CMU Hospital, and is now Board Member of CMU and a member of the Executive Committee of the World Federation of Acupuncture-Moxibustion Societies. He was awarded the Certificate of World’s Famous Doctor Award in 2001.",coeditorTwoBiosketch:"Dr. Hung is a pioneering researcher in the physical study of meridian and holder of a registered patent for needle improvement with a supercritical fluid-treated needle. With a Ph.D. degree from the Chang Gung University and awarded the Research thesis of scholarship in Integrate Traditional Chinese and West medicine in 2009, his clinical practice in Chinese medicine including acupuncture spans 25 years.",coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"49848",title:"Dr.",name:"Wen-Long",middleName:null,surname:"Hu",slug:"wen-long-hu",fullName:"Wen-Long Hu",profilePictureURL:"https://mts.intechopen.com/storage/users/49848/images/system/49848.jpg",biography:"Wen-Long Hu is Chief of the Division of Acupuncture, Department of Chinese Medicine at Kaohsiung Chang Gung Memorial Hospital, as well as an adjunct associate professor at Fooyin University and Kaohsiung Medical University. Wen-Long is President of Taiwan Traditional Chinese Medicine Medical Association. He has 28 years of experience in clinical practice in laser acupuncture therapy and 34 years in acupuncture. He is an invited speaker for lectures and workshops in laser acupuncture at many symposiums held by medical associations. He owns the patent for herbal preparation and producing, and for the supercritical fluid-treated needle. Dr. Hu has published three books, 12 book chapters, and more than 30 papers in reputed journals, besides serving as an editorial board member of repute.",institutionString:"Kaohsiung Chang Gung Memorial Hospital",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"11",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"Kaohsiung Chang Gung Memorial Hospital",institutionURL:null,country:{name:"Taiwan"}}}],coeditorOne:{id:"452002",title:"Dr.",name:"Mao-Feng",middleName:null,surname:"Sun",slug:"mao-feng-sun",fullName:"Mao-Feng Sun",profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:"Mao-Feng Sun is former Dean of College of Chinese Medicine in China Medical University (CMU) and former Chinese Medicine Vice Superintendent in China Medical University Hospital. He has been recently recruited as a Board Member of CMU as an experienced Chinese Medicine Doctor with expertise in acupuncture spanning over 30 years. He is also an Executive Committee of the World Federation of Acupuncture-Moxibustion Societies, representing Taiwan on acupuncture-related matters. He was awarded the Certificate of World’s Famous Doctor Award by The 21st Century Congress of Natural Medicine in May 2001. Not only is he a professor at CMU, but also a visiting professor in various institutions, including the American College of Acupuncture & Oriental Medicine (ACAOM), Nanjing University of Chinese Medicine, and Guangzhou University of Chinese Medicine.",institutionString:"China Medical University",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"China Medical University",institutionURL:null,country:{name:"Taiwan"}}},coeditorTwo:{id:"49804",title:"Dr.",name:"Yu-Chiang",middleName:null,surname:"Hung",slug:"yu-chiang-hung",fullName:"Yu-Chiang Hung",profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:"Professor Dr. Yu-Chiang Hung was born on the 5th of January 1965 in Taiwan. He was currently serving as an attending doctor and academic professor in the Kaohsiung Chang Gung Memorial Hospital. He has been a director of the Department of Chinese medicine for 6 years. He graduated with a Bachelor's degree from the China Medical University in 1990, an M.D., degree from the National Yang-Ming University in 1992, and a Ph.D. degree from the Chang Gung University in 2010. Professor Dr. Hung was awarded “Research thesis of scholarship” in Integrate Traditional Chinese and West medicine 2009 in Taiwan and “Outstanding Scientist Award” on Engineering, Science and Medicine 2021 in India. His experiences in clinical practice in traditional Chinese medicine including acupuncture spans about 25 years. He holds a patent for needle improvement with a supercritical fluid-treated needle. Professor Dr. Hung has published 65 papers in SCI reputed journals and 12 book chapters.",institutionString:"Kaohsiung Chang Gung Memorial Hospital",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"9",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"Kaohsiung Chang Gung Memorial Hospital",institutionURL:null,country:{name:"Taiwan"}}},coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"16",title:"Medicine",slug:"medicine"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"347259",firstName:"Karmen",lastName:"Daleta",middleName:null,title:"Ms.",imageUrl:"//cdnintech.com/web/frontend/www/assets/author.svg",email:"karmen@intechopen.com",biography:null}},relatedBooks:[{type:"book",id:"6550",title:"Cohort Studies in Health Sciences",subtitle:null,isOpenForSubmission:!1,hash:"01df5aba4fff1a84b37a2fdafa809660",slug:"cohort-studies-in-health-sciences",bookSignature:"R. 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"72",title:"Ionic Liquids",subtitle:"Theory, Properties, New Approaches",isOpenForSubmission:!1,hash:"d94ffa3cfa10505e3b1d676d46fcd3f5",slug:"ionic-liquids-theory-properties-new-approaches",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/72.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"314",title:"Regenerative Medicine and Tissue Engineering",subtitle:"Cells and Biomaterials",isOpenForSubmission:!1,hash:"bb67e80e480c86bb8315458012d65686",slug:"regenerative-medicine-and-tissue-engineering-cells-and-biomaterials",bookSignature:"Daniel Eberli",coverURL:"https://cdn.intechopen.com/books/images_new/314.jpg",editedByType:"Edited by",editors:[{id:"6495",title:"Dr.",name:"Daniel",surname:"Eberli",slug:"daniel-eberli",fullName:"Daniel Eberli"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"57",title:"Physics and Applications of Graphene",subtitle:"Experiments",isOpenForSubmission:!1,hash:"0e6622a71cf4f02f45bfdd5691e1189a",slug:"physics-and-applications-of-graphene-experiments",bookSignature:"Sergey Mikhailov",coverURL:"https://cdn.intechopen.com/books/images_new/57.jpg",editedByType:"Edited by",editors:[{id:"16042",title:"Dr.",name:"Sergey",surname:"Mikhailov",slug:"sergey-mikhailov",fullName:"Sergey Mikhailov"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1373",title:"Ionic Liquids",subtitle:"Applications and Perspectives",isOpenForSubmission:!1,hash:"5e9ae5ae9167cde4b344e499a792c41c",slug:"ionic-liquids-applications-and-perspectives",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/1373.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"67934",title:"Bupivacaine Pharmacokinetics in Pregnant Women",doi:"10.5772/intechopen.87184",slug:"bupivacaine-pharmacokinetics-in-pregnant-women",body:'Pregnancy and labor are accompanied by important physiological and anatomical changes. There is a modification in the metabolism of drugs and changes in their pharmacokinetics as well as their interaction with organs and systems. Anesthesia in the obstetric patient is influenced by physiological changes, concomitant diseases, and preferences for a specific drug. Local anesthetics are a special topic due to the frequent use of them during labor, the performance of cesarean section, or another non-obstetric procedure in the pregnant patient. It is necessary to know the pharmacokinetics of the local anesthetic most frequently used in our practice, bupivacaine, plain or hyperbaric, or one of its enantiomers. The objective of this review is to know the main studies that have evaluated pharmacokinetics and their interaction with systems and organs in the mother and placental passage.
During pregnancy many hemodynamic and hormonal changes occur like cardiovascular adaptations such as increased heart rate, plasmatic volume, cardiac output and sympathetic tone, or a reduction in peripheral resistances. The heart moves to the left and up during pregnancy, since the diaphragm progressively rises through the gravid uterus. These changes may be more important in post-term periods that are defined as pregnancies greater than 294 days (≥42 weeks of gestation periods) [1]. The increase in cardiac output and blood volume may increase the distribution of some drugs; the water-soluble ones will increase in their absorption as well as the liposoluble by the augmentation of the maternal fat, and there is an increase of the glomerular filtration and the renal sanguineous irrigation, which will produce an increase in the clearance of the drug [2].
The blood volume increases by 30–50%, and this rise begins in the first trimester and continues rising until week 30 of gestation and returns to its normal volume after pregnancy. A phenomenon is a dilutional anemia since the proportion of plasma volumes in relation to blood volume increases proportionally greater than red cells, and the hemoglobin concentrations will vary between 11 and 12 g/100 mL at the end of pregnancy. The increase in plasma volume is related to the size of the fetus; one theory is that the adrenal glands of the fetus can initiate an increase in blood volume by providing dehydroepiandrosterone (precursor of estrogen) to the placenta, stimulating the liver to produce angiotensin, which increases aldosterone production and fluid retention [3].
Increased blood volume and increased cardiac output may respond to an initial vasodilation caused by a vasodilating substance that may be prostacyclin or the endothelial-derived relaxing factor. This increase in blood volume is necessary to meet the needs of the fetus and compensate for the loss of maternal blood at delivery; the mother can lose up to 20% of their blood volume without a significant change in his hematocrit [3]. Cardiac output increases to 30–50% during pregnancy, peaks at weeks 28–32, and then decreases a little during the last weeks. The values increase to 4.5–6.5 L/min and decrease as the term of pregnancy approaches but are considerably lower in the lateral position than in the supine position. The supine position during labor is associated with an 8% incidence of hypotension, and 15–20% of patients will have aortoiliac and vena cava compression. The reduced cardiac output lowers uterine blood flow, and this adversely affects the fetus. The cardiac return is diverted from the vena cava through the vertebral and azygos systems to the superior vena cava, and this enlarges the epidural veins and provides an explanation for the reduced amount of local anesthetic needed for spinal or epidural analgesia in pregnancy, and there is an increase in sympathetic activity that results in vasoconstriction that reduced the degree of hypotension observed [4].
Uterine blood flow increases to 200 mL/min by week 28 and 500 mL/min by the end of pregnancy, the uterine musculature receives approximately 20% of the total uterine blood flow, while the area of the placenta receives 80% by what to the placenta, that is to say, 400 mL of blood per minute or approximately 80 mL of blood per 100 g of tissue per minute [4].
Bupivacaine is a local anesthetic amide type, synthesized in 1957 by Ekenstam in Switzerland, and has a mechanism of action through the obstruction of sodium channels to the nerve membrane, preventing the generation of an action potential. It is used for intraoperative local anesthesia, postoperative analgesia, and chronic pain treatment. It is widely used in pregnant patients and provides excellent sensory anesthesia with reported concentrations at 0.5% [5].
The effectiveness of bupivacaine was evaluated by the toxicity, the latency, and the degree of motor block, the sympathetic block, and the sensory block, as well as the elimination time. The absorption and distribution are influenced by the vascularity of the injection site, the mode of injection, and the degree of ionization of the drug. After IV administration, its half-life is 45 min corresponding to redistribution and 2.5 h due to elimination. It is metabolized by the liver by N-dealkylation and glucuronide conjugation. Elimination is urinary. Although some metabolites are eliminated via the pulmonary and bile fluid, the portion bound to proteins is the active part, and the unbound is responsible for the toxic effects [5].
The pharmacokinetics in the mother-fetus binomial changes, the fetus and the placenta function as deposits, the placenta has the capacity to metabolize drugs, and it is possible to modulate the elimination of the drug by producing metabolites and retaining large quantities for its release back to the fetus [6].
The apparent volume of distribution increases during pregnancy with the increase in plasma volume, approximately 40–50% from the beginning of pregnancy to a maximum of 32 weeks. During the placental growth phase, the peripheral hairy surface increases from 3.7 m2 in week 25 to 11 m2 during the last month of gestation, and the fetal-mother exchange surface decreases from 92 to 767 m2 due to a decrease in density of the microvilli [6].
Since the drugs that cross the placenta reach the fetus via the umbilical venous blood and 50% of it enters the liver circulation and the rest goes through the venous duct, then half of the transported drug is susceptible to hepatic metabolism and the other half enters the fetal circulation directly. The distribution of a drug in the fetus is regulated by variations in pH and protein binding [6].
The drugs once inside the organism move between the compartments, and to analyze it the changes in the concentration of the drug in a compartment as a function of time are studied, according to the following formula [7]:
where dC/dt equals the change in concentration in relation to time and −kCn refers to the decrease in the concentration of a drug which is an exponential type function [7].
When the rate of change is independent of the concentration of the drug, it is called a zero-order process, and when the process and the rate of change are proportional to the concentration of the drug, it is called a first-order process, the mother-fetus, which behaves like a model of two compartments with bidirectional distribution [7].
Bupivacaine has an asymmetric carbon atom and can take the form of two enantiomers (R + dextrobupivacaine and S-levobupivacaine), form different three-dimensional relationships in the asymmetric medium of receptors and enzymes, and result in differences in toxicity, distribution, cardiotoxicity, and neurotoxicity [8]. Levobupivacaine is soluble in water with a molecular weight of 325, a partition coefficient of 1624, and a pKa of 8.09. Both the partition coefficient and the pKa are very similar to those of bupivacaine. Its pH is 4.0–6.5. Its maximum plasma concentration reaches 30 min, and its volume of distribution is 67 L [8]. Liposomal bupivacaine is composed of multivesicular liposomes with 10–30 micrometers in diameter and has a duration of analgesia of up to 72 h [9].
Bupivacaine has a pKa of 8.1, ionized fraction of 15% at a pH of 7.4, fat/buffer coefficient of 115, protein binding 95%, molecular weight of 288 Daltons, and an effective anesthetic concentration in the rat sciatic nerve of 0.25. The main determinant of adverse systemic effects is the free fraction, which is not bound to proteins [10].
Spinal anesthesia involves changes in the mother’s hemodynamic, including decreased venous return, decreased systemic vascular resistance, and a compensatory increase in cardiac output. These changes increase the risk of intraoperative arrhythmias in patients [1].
Local anesthetics routinely used include bupivacaine and its enantiomer levobupivacaine, the latter having a clinical profile close to bupivacaine, but it is less toxic to both the nervous system and the cardiovascular system, which makes it useful in obstetric anesthesia, where large volumes of local anesthetics may be required. It has been reported that bupivacaine and levobupivacaine cause a concentration-dependent inhibition of the amplitude of gravid myometrial contractions in rats [11].
Local anesthetics are amphiphilic and can enter a variety of cellular compartments and potentially interact with many different cell membranes, organelles (including the inhibition of mitochondrial adenosine production), and a variety of membrane junctions and charged cytosol molecules. Other mechanisms, which can contribute to myometrial inhibition, include the blocking of ionotropic signaling pathways (sodium, potassium, or calcium) and interference with protein modulation of calcium and potassium channels [11].
The practice of using low concentrations (0.125–0.25%) makes it less likely that the inhibitory concentrations in the plasma reach the clinical practice [11]. The toxic effect of local anesthetics on myocardial contractility and cardiac conduction is due to the alteration of the calcium channel [12]. In a study by Mahmut et al., 40 healthy pregnant patients were included; they evaluated QT interval, which increased significantly in the post-term group, which makes them susceptible to the development of arrhythmias; and they concluded that care must be taken during the induction of spinal anesthesia in term pregnancies as well as cardiovascular monitoring should be prolonged in this type of patients [13].
The Dogan et al. study used 12 mg of 0.5% hyperbaric bupivacaine or 0.5% of levobupivacaine for the spinal levobupivacaine group and calculated the QTc with the Bazzett formula and the QT dispersion (difference between the maximum and minimum QTc). They studied 60 patients. The mean maximum QTc was longer in levobupivacaine, and the minimum mean QTc was also longer. In the bupivacaine group, the maximum QTc was longer than levobupivacaine [14].
It is known that the placenta does not limit the fetal transfer of local anesthetics administered to the mother; using a human placental model in rats, it is suggested that bupivacaine accumulates in the placenta [15]. The study of Morishima et al., a study in the University of Columbia with a model of rats, administered 1 mg/kg of bupivacaine followed by an infusion of 0.33 mg/kg/min, over a total period of 15 min. The maximum dose of bupivacaine was 1200–1400 ng/mL, which is similar to the concentration of plasma bupivacaine in pregnant women under cesarean section with epidural anesthesia [1].
The pharmacokinetic analysis of bupivacaine was assumed as an open two-compartment model. A transient reduction in heart rate occurred during the infusion of bupivacaine [1].
The mean peak concentration of bupivacaine in maternal plasma was 3123 ± 370 ng/mL, the concentration decreased to 26 ± 12 ng/mL at 180 min, and after 240 min, it became undetectable. In plasma 4′-hydroxybupivacaine and 2,6-pipecoloxylidine were not detected. The half-life of distribution was 37.7 ± 2.4 min, the volume of distribution in stable state 3.86 ± 0.29 l/kg, and the total clearance 93.3 ± 8.6 mL/min−1.kg−1; other parameters were K12 0.462 ± 0.066; K21 0.081 ± 0.008 and K10 0.166 ± 0.021. In fetal plasma, a bupivacaine peak of 320 ± 38 ng/mL was detected rapidly, and the drug became undetectable at 4 h. A bupivacaine concentration of 4817 ± 976 ng/g in the amnion at the end of the infusion was the highest sample of those obtained at any time [1].
While the dose of bupivacaine decreases, 3-hydroxybupivacaine remains virtually constant in the amnion and myometrium, and the 3-hydroxybupivacaine also kept increasing. Despite a high concentration of 3-hydroxybupivacaine in these tissues, the amniotic fluid concentration was not as high as expected. The 4-hydroxybupivacaine and the 2.6 pipecoloxylidide were only detected in traces in samples obtained in 2 h. The largest metabolite detected in rats was 3-hydroxybupivacaine [1].
In the fetus, the 3-hydroxybupivacaine remains detectable in the liver up to 4 h, while it virtually disappears from other tissues, because most of the umbilical venous blood perfused in fetal liver, and bupivacaine transmitted to the fetus, can directly enter the fetal liver; this may suggest that the fetal liver is capable of metabolizing bupivacaine. However, because polar metabolites do not cross the placental membrane bidirectionally, 3-hydroxybupivacaine probably accumulates in the fetus [1].
In the study by Eslamian et al., a randomized, double-blind, placebo-controlled study of 50 pregnant women under elective cesarean section, transverse abdominis plane (TAP) block was used. The preparation was performed with 40 mL of 0.25% hyperbaric bupivacaine plus 2 mL of normal saline for the placebo group of 400 mL of 0.25% hyperbaric bupivacaine plus 2 mL of sufentanil for the study group. The block was guided with ultrasound; the patients who received 40 mL of hyperbaric bupivacaine 0.25% plus 10 μg of sufentanil consumed less morphine during 24 h after surgery compared to the control group (p = 0.002); the mean difference in morphine consumption was 15.6 mg in the first 24 h of the postoperative period. There were no differences in the EVA scale between one group and another with>0.05 [15].
In the Trabelsi et al. study, a group of 17 pregnant patients were administered with spinal anesthesia with hyperbaric bupivacaine with 5 μg of sufentanil, and abdominal ultrasound-guided TAP block was placed with 20 mL 0.25% bupivacaine bilaterally. They found an accumulated average of bupivacaine of 1.4 ± 0.2 mg/kg (range of 1.05–1.79 mg/kg); the CMAX was 802.36 ng/mL (231.8–3504.5 ng/mL) and was reached at 30 min (TMAX). The mean area under the curve (AUC) (0–24 h) was 4505.4 ng/mL, and the elimination half-life was 8.75 h for bupivacaine, demonstrating that bilateral blockade increases the total concentration of bupivacaine in the plasma after administering spinal anesthesia with bupivacaine. Plasma concentrations occurred at 30 min after injection, all peak concentrations were reached between 10 and 90 min and a second delayed peak of 90 min [10].
In the Lacassie study, in 12 pregnant women and 11 healthy volunteers, the transverse muscle was blocked with levobupivacaine 0.25%, 20 mL with epinephrine 5 μg/ml−1, venous concentrations were 2.62 mg/L−1, below the level toxic, the volume of distribution of levobupivacaine was 172 L (70 kg) (IC 95% 137–207) higher than in healthy volunteers [16].
The Stourac study worked with pregnant women under epidural analgesia; they used 12.5 mg of bupivacaine and 5 μg of sufentanil in 10 mL of normal saline, and boluses of half the dose every 60–90 min were administered. Another group using PCA pumps with remifentanil connecting a 50 mL syringe with remifentanil at a concentration of 20 μg/mL studied a total of 24 patients, and there was no significant difference between the groups. The level of satisfaction of the patients was 88% with epidural analgesia and 85% with PCA pump. Among the complications, only one had hypotension, with remifentanil, and experienced drowsiness and dizziness as well as temporary anxiolysis [8].
In the Chen et al. study, they determined the lowest effective concentration of levobupivacaine and levobupivacaine with fentanyl, and one group received 1.2 mg/mL of levobupivacaine and 2 μg/mL of fentanyl. They determined that the concentrations of 0.6 mg/mL of levobupivacaine plus 2 μg/mL of fentanyl and 1 mg/mL of levobupivacaine were the lowest concentrations of the drugs required for effective analgesia, and they analyzed a total of 83 pregnant women and showed that levobupivacaine alone produces a comparable analgesia with levobupivacaine with narcotic; in addition, those who received narcotics had more adverse effects [17].
In the Fanning et al. study, pregnant patients received spinal anesthesia with 10–12 mg at 0.5% hyperbaric bupivacaine with 20–25 μg of intrathecal fentanyl and 100–150 μg of intrathecal morphine. After the placental extraction, a small segment of the myometrium was removed from the incisional surface of the lower uterine segment. Each sample was dissected in four longitudinal muscles. The muscle was exposed to bupivacaine or levobupivacaine and chemical contractions were induced. Eight muscle samples were included. Bupivacaine and levobupivacaine caused a concentration-dependent decrease in the amplitude of the contractions reaching a statistical significance of p = 0.002 for bupivacaine and p = 0.001 for levobupivacaine compared to the control period before the administration of any drug [18]. There was no significant difference between bupivacaine and levobupivacaine in its effects on contraction of the myometrium, in the amplitude of the contractions, and in the interval between contractions for bupivacaine and levobupivacaine; there was no difference between the EC50 (effective concentration 50) and the effect of both drugs in contractility which was reversible. No increase in contractile amplitude was observed. The maximum concentrations in plasma were 1053 μg/mL (3.24 × 10–6 m) for bupivacaine and 1017 μg/mL (3.13 × 10–6 m) for levobupivacaine. They concluded that bupivacaine and its enantiomer levobupivacaine cause a similar decrease in concentration-dependent contractions. The concentrations required for their inhibitory effect on the amplitude of the contractions were much higher (33 times) than the clinically relevant plasma concentrations of these drugs after epidural administration and are unlikely to be significant in the low epidural dose scenario to analgesia in labor periods [18].
The combination with clonidine, a partial agonist of alpha 2 adrenergic receptors, interacts with the local anesthetic in the neural axis. The analgesic effect is due to its action in spinal and supraspinal α-adrenergic receptors, including the activation of postsynaptic α-2 receptors, since the noradrenergic descending pathways of cholinergic neurons and the release of nitric oxide and substances such as enkephalin reduce the absorption of local anesthetics by a vasoconstrictor effect, improving quality and increasing the duration of anesthetic blockade. It is recommended at doses of 1 μg/kg combined with bupivacaine [12]. In a Brazilian study, 66 pregnant patients were divided into two groups: a group with 8 mg of bupivacaine +75 μg of clonidine and 100 μg of morphine +0.9% saline and another group with 10 mg of bupivacaine +75 μg of clonidine +100 μg of morphine + saline 0.9%; the total volume administered was 4 ml in both groups, and there was no difference in hemodynamic parameters, adverse effects, and level of consciousness, only the regression time of the motor block, in group 1, of 198.48 ± 47.63 min, and in group 2 of 232.84 ± 63.66 min; p = 0.00073. They concluded that morphine and clonidine at low doses produce adequate postoperative analgesia in pregnant patients [12].
In the study Zhan et al., 70 pregnant or obstetric patients were studied; 0.5% spinal isobaric bupivacaine was 4 mg; the ED50 of intrathecal bupivacaine for motor block was 3.96 mg (IC 95% 3.83–4.98) for pregnant women versus 4.51 mg (95% CI 4.27–4.76) for nonpregnant women. The potency of bupivacaine for motor block in pregnant versus non-pregnant women was 1.14 times higher (95% CI 1.05–1.24). This is because the supine position can increase the dissemination of the injected drugs due to the increase in intra-abdominal pressure, in addition to the increase in blood flow in the vasculature in the epidural veins, which distends and compresses the intraspinal space decreasing the volume of the spinal fluid cerebral [19].
The analysis of the placental intervillous space shows to be an appropriate place of investigation because this space is initially filled with blood coming from the maternal spiral arteries that interchange with the fetal venous blood, when the blood of the mother flows toward the branched villi. Although it is an important interchange interface, the intervillous space has been studied as the transport of substances between the mother, the placenta, and the fetus; obtaining blood from this compartment has provided a unique opportunity to study the maternal-fetal physiological relationship in a more physiological way [20]. The importance of this is that the reduced ability of the fetus to eliminate drugs can cause prolonged effects on the fetus, since half of the fetal circulation reaches the umbilical vein and directly reaches the fetal heart and brain by passing to the fetus. Liver immaturity contributes to the presentation of adverse effects, the fetus eliminates the drug by diffusion into the maternal compartment, although the majority of the metabolites are more polar and it is unlikely that the placental membrane crosses the placental membrane back to the compartment maternal, possibly resulting in the accumulation of metabolites in various fetal tissues [20].
In the study by Barros et al., a Brazilian study, the concentrations of bupivacaine and lidocaine as well as its metabolite (MEGX) and its placental transfer were analyzed in 10 healthy pregnant patients, under elective cesarean and epidural anesthesia. The administration of the medication was epidural of 0.1 mg of fentanyl citrate, 112.5 mg of 0.5% bupivacaine with 2:200000 epinephrine, and 200 mg of lidocaine 2% without vasoconstrictor injected into the epidural space [11]. The concentrations of bupivacaine enantiomers were high in the maternal plasma and placental intervillous space than in the umbilical vein and the umbilical artery. The concentrations of S-bupivacaine in the maternal plasma were higher than the R-bupivacaine concentrations, and the values were 195.2 and 186.0 ng/mL. There were no significant differences (P < 0.05) between their concentrations in umbilical fetal vessels [11]. The placental transfer was 33% for R-bupivacaine and 31% for the S-bupivacaine. The concentrations of the enantiomer S-bupivacaine were 3.5 and 3.82 times higher in the placental intervillous space than that of the umbilical vein and the umbilical artery, respectively [11].
The R-bupivacaine concentrations were 2.9 times higher in the placental intervillous space than the fetal umbilical vein concentrations and 3.16 times higher than the concentrations in the fetal umbilical artery. There were no cardiocirculatory changes, neonatal repercussions in the APGAR, or respiratory depression. There was no significant difference in the ratio of enantiomer concentrations between the different compartments, maternal or fetal. This study showed that the intervillous space acts as a drug reservoir [11].
In conclusion, local anesthetics, including bupivacaine, are among the drugs most commonly used in clinical practice for the management of pregnant patients for obstetric or non-obstetric procedures. It is essential to know the pharmacokinetics of the drug in order to understand the concentrations of the drugs which we can obtain adequate analgesic and anesthetic effects, trying to diminish the toxic effects.
I thank the Instituto Nacional de Cardiología Ignacio Chávez for allowing me to carry out my work, promoting research and dissemination of knowledge.
I declared that I do not have any conflict of interests.
Conventional alloys are usually based on one main element. To improve the structural and functional properties of the alloy, other elements can be added. However, this strategy leads to the formation of several phases. Indeed, physical metallurgy and phase diagrams show that multifunctional alloys can develop dozens of structures with several phases. Structurally, they can be fragile, and scientifically their analysis will be difficult. On the other hand, high entropy alloys (HEAs) [1, 2] are characterized by high mixing entropy. Therefore, they have become primordial structures for developing potential applications tanks to their superior properties. HEAs materials are characterized by four effects: high entropy, severe lattice distortion, slow scattering and the cocktail effect. They are detailed in the reference [3]. Excellent properties of HEAs have been reported such as outstanding thermal stability [4], good wear resistance [5], good corrosion resistance [6] and best oxidation resistance [7].
On the other hand, the surface is seen as an important component of the material for developing industrial applications. It can be easily modified and adapted to improve the performance of the materials according to demanding conditions. Thus, the quality of the material surface has a significant impact on its lifetime. Thin films are found in many applications with improved surface properties for high-performance materials. For example, tools used in machining are often coated with protective and hard thin films to achieve high mechanical properties and better wear resistance [8, 9, 10]. Better physical properties such as a good oxidation resistance are also required for aerospace and automotive applications. Protective films can also be found in biomedical applications such as bio-implants [11, 12]. Review articles have been reported on the effect of process parameters on the phase structure of HEFs with also a discussion on the preparation process and the functional properties of the films [13]. Others have been focused on the development of HEAs/HEFs operating in extreme conditions and other characteristics [14, 15, 16].
Magnetron sputtering is a widely used technique to deposit thin films. It is used in several industrial applications. This technology has been continuously developed to improve the target utilization and increase the deposition rates by reducing operating costs. Preparing high entropy films (HEFs) by this technique is of considerable interest to provide coatings with superior properties. To this end, several research works report on the development of coatings with improved performances but with low-cost materials. Conventional hard coatings, such as traditional nitrides and carbides, have shown the potential to increase wear resistance. However, these traditional materials seem to not meet the current needs. For example, some traditional nitrides have a limited oxidation resistance. Recently, HEFs have shown much improved performances. A comparison of different alloys is presented in the reference [17] where the oxidation resistance of an HEF reaches 1300°C. (AlCrNbTaTi)N HEF shows an oxidation resistance at 850°C for 100 hours [18] which is better than various traditional nitrides. Many HEFs, prepared by magnetron sputtering technique, revealed other excellent performances [19, 20, 21, 22].
By using magnetron sputtering technique, various deposition parameters are exploited to control the properties of HEFs. Among these parameters, we find gas flow rate, substrate temperature, working pressure, and bias voltage. The chapter overviews magnetron sputtering process, the classes of different HEFs and it shed light on the effect of the different parameters on the properties of HEFs. Applications of some HEFs are also presented.
There are several ways to prepare thin films. The most common methods used in research laboratories and in industry are PVD and CVD techniques. Among the PVD procedures, magnetron sputtering shows several advantages. It offers the possibility to obtain a stoichiometry like that of the used target. The quenching rate is high (109 K/s) leading to the formation of sutured solid solutions. In the following paragraph, the process of the magnetron sputtering will be briefly introduced.
The synthesis of coatings by using magnetron sputtering technique can be done in three steps. In the first step, an atomic vapor is created by extracting the atoms from the target thanks to applied potential difference between the target and the reactor walls. Then this vapor is transferred to the substrate in a rarefied atmosphere of chemically neutral gas. In the last step, the atomic vapor condenses into the substrate surface allowing the germination process and consequently the growth of the film.
This basic process is limited by various effects like low deposition rate, low ionization coefficient in the plasma, and a substrate heat. To circumvent these limitations, a magnetron dispositive is integrated into the process. The magnets are placed behind the cathode. They generate a magnetic field parallel to the surface of the target, perpendicular to the electric field. The electrons emitted by the cathode and present in the gas and are trapped by the field lines (Figure 1). The probability that an electron meets argon is so high. The ion bombardment of the target results in a higher sputtering rate and the deposition rate increases.
Magnetron sputtering process.
The difference between the High Power Impulse Magnetron Sputtering (HiPIMS) and DCMS is the use of high power densities. HiPIMS is a recent advance in sputtering process using magnetron sputtering with a high voltage power source. High voltage with short duration is used to generate high-density plasma resulting in high degree of ionization of the coating material. HiPIMS, has various advantages. The highly energetic ions, produced by high voltage, result in denser film compared to that deposited by conventional techniques. HiPIMS bombards the sample with high-energy gas ions that can remove oxides and therefore clean the surface. This can improve the adhesion of the coating to the surface. A description of plasma process using HiPIMS can be found in Anders’s tutorial [23].
Few studies have been reported in the literature on using HiPIMS to prepare the HEFs. The papers revealed the formation of dense microstructures of the films compared to that obtained by DCMS process. The change of the microstructure strongly influences the mechanical and electrochemical performances of HEFS. For example, Bachani and co-workers [24] investigated (TiZrNbTaFe)N using HiPIMS process and found that the film containing 32 at.% of nitrogen exhibits a very dense microstructure compared to others. Its hardness is improved (36.2 GPa). The corrosion resistance is increased, according to the variation of the nitrogen content, due to the densification of the films. CuNiTiNbCr dual-phases were formed at different working pressures as reported by Li and co-workers [25]. AlCrTiVZr HEFs have been studied under the effect of nitrogen. Due to its densification, the nitride obtained at 12 sccm presents a hardness of 41.8 GPa which is the super-hard film compared to others. Figure 2 presents SEM images showing the difference in the morphology of (AlCrNbSiTiV)N films obtained by both processes DCMS (Figure 2a, b) and HiPIMS (Figure 2c, d) [26].
SEM images showing the surfaces and cross-sectional microstructure of (AlCrNbSiTiV)N deposition using DCMS (a,b) and HiPIMS (c,d). The figure is reproduced with permission of [
HEFs can be classified into three categories: metallics, ceramics and composites films as presented in Figure 3.
Classes of HEFs.
Metallic HEFs: they consist basically of Cantor-based elements. They are mostly composed of transition elements such as Al, Cr, Fe, Ti, Mo, etc. Refractory elements are also used to develop coatings for high-temperature applications. The refractory elements, such as Hf, Ta, Nb, V, W, etc have much higher melting point. These materials are classified into HfNbTaZr, CrMoNbTa [27].
Ceramic HEFs: consist of nitrides, carbides, oxides and borides. These materials can be deposited on substrates by using reactive mode (introduction of gas). Solid solutions are reported and strong nitride-, carbide-, oxide-forming elements like Zr, Cr, Si and Ti are used. These ceramics exhibit superior properties such as high oxidation resistance, good corrosion resistance and high tribological performances.
Composite HEFs: These materials can be prepared by reinforcing the film matrix with ceramics. Various ceramics like WC, TiC, NbC, and others have been used as reinforcements to improve the properties of HEFs. Metallic reinforcements have been also used. For example, Tian and co-workers [28] prepared a compact ACoCrniFeTi/Ni coating with Ni splats uniformly distributed in the matrix (ACoCrniFeTi). Due to this reinforcement, the results reveal an improvement in its tensile test compared to that of the matrix alone.
DCMS was largely used to prepare the HEFs under different conditions. The most-reported films have three different morphologies, columnar, dendrite-like and fibrous-like. The deposition parameters are reported to have a strong influence on the HEFs morphology. The mobility of particles into the surface of the substrate is the main reason of resulted morphology of the films. Studies have reported the effect of gas mixture on the films properties. Nitrogen, carbon and oxygen are used to form high entropy ceramics. For example, AlCrNbYZr exhibits dendrite-like morphology. By adding the nitrogen (AlCrNbYZr)N films reveal V-shaped columnar morphology. Zhang et al. [29] studied the effect of nitrogen on CrNbTiAlV films. Smooth surface and dense cross-sectional morphology are observed in the metallic film (CrNbTiAlV). With addition of the nitrogen, (CrNbTiAl)N gradually changes into columnar morphology. Some carbides show a different trend. Jhong et al. [21] studied CrNbSiTaZr as a function of CH4 flow rate. They show that all films exhibit smooth surface and featureless cross-sectional morphology. The mobility of the atoms on the surface can be the main reason for the formation of dense structures. Oxygen gas also influences the morphology of HEFs. In the case of AlCoCrCu0.5FeNi, the films exhibit agglomerated grains at a low oxygen flow rate. However, as the oxygen flow increases the grains become equiaxed with a size of 35 nm.
The morphology of HEFs can be also influenced by other parameters like the pressure and the bias voltage. AlCrTiWNbT shows a columnar morphology when the bias voltage changes from −50V to −100V but at −150V fine spaced striation lines are formed of the film [30]. Fine fibers morphology is formed for CrNbSiTiZr at −50V which is transformed to compact at −200V [31].
For the structure, the prepared HEFs by magnetron sputtering are reported to have amorphous or crystalline structure. The most crystalline structures exhibit fcc solid solution. The structure can change under the effect of various parameters such as the high entropy and the atomic mismatch. The high entropy promotes the formation of the solid solution instead of metallics compounds. However, if the difference in atomic mismatch is enough, the film remains amorphous. In the case of HEFs by magnetron sputtering, three different structures are reported: amorphous, fcc and bcc. AlCoCrNi [32], NbTiAlSiZr [33] and FeCoNiCuVZrAl [34] HEFs exhibit an amorphous structure which remains unchangeable even after adding the nitrogen. On the other hand, other studies revealed the phase transformation from amorphous to crystalline structure upon increasing the nitrogen contents in the films. Cheng et al. [22] examined the effect of nitrogen on AlCrMoTaTiZr by varying its flow rate from 0% to 50%. The percentage of the flow rate is calculated according to argon quantity by the followed formula RN=N2/(Ar+N2). The results show that the film exhibits an amorphous structure at RN=0%. However, when the nitrogen flow increases fcc-single phases structures are formed as is presented the Figure 4.
X-ray diffractogramme of (AlCrMoTaTiZr)N as function of nitrogen flow rate (N2). The figure is reproduced with permission of [
The nitrogen atoms are adsorbed in interstitial sites leading to the formation of nitrides. The interaction between the nitrogen and the elements varies along with the periodic table. Group 4–6 are strong nitride former while metals in group 7–11 are weakly nitride former. This interaction has a mix of ionic, metallic and covalent bonding. The reported HEFs nitrides have NaCl-type structure as mentioned above. Because of the similarities of the structure between different standard nitrides, extended homogeneity regions for solid solutions can be obtained.
Among other ceramics, carbides can be also prepared. Up to now, they have not been widely investigated like the nitrides. Most references focus on the use of strong carbide forming metals. Kuang et al. have investigated the tribological properties of CrNbTiMoZr carbide films [35]. Kao and co-workers studied the effect of carbon content on the mechanical and electrochemical properties of CrNbSiTaZr films [36]. There is also others few studied on the same subject [21, 37].Figure 5 shows XRD diffractograms of (CrNbSiTiZr)Cx films as a function of CH4 rate flow. In the case of carbides, textured solid solutions are also formed. (111), (200), (220) and (311) peaks of the prepared films reveal the formation of fcc NaCl-type structure (Figure 5).
X-ray diffractogramme of (CrNbSiTiZr)Cx as function of nitrogen flow rate (N2). The figure is reproduced with permission of [
X-ray photoelectron spectroscopy (XPS) is a powerful technique to provide information on the composition and the chemical binding between the elements. Up to date, few XPS analysis are reported on HEFs studies. More efforts are needed to provide more information on the binding nature and the compound of different elements constituting HEFs.
Khan et al. [38] examined AlCoCrCu0.5FeNi nitride films by XPS. They showed that the porosity of films grows with a higher nitrogen flow fraction facilitating than the atmospheric oxidation. XPS analysis confirmed the formation of protective oxides AlO3, CrO3 and nitrides AlN and CrN on the films surfaces [38].
Khan and co-workers [38] used XPS to determine the oxidation states of AlCoCrCu0.5FeNi HEFs. The films were deposited at various nitrogen flow rates. The results revealed the formation of both nitrides and oxides on the surface of the films. At higher nitrogen flow, binary oxides Al2O3 and Cr2O3 were formed together with nitrides AlN and CrN on the films surfaces. Feng and coworkers [39] studied (ZrNbTaTiW)N HEFs and reported by XPS the formation of a mixture of metallic (Nb, W, Ta), nitride (ZrN, TiN, TaN) and oxide ZO2.
Our group studied the nitridation effect on AlTiTaZrHf, prepared by the magnetron sputtering technique [40]. All the elements are nitride after adding the nitrogen. As the nitrogen flow rate increases, the nitride content changes according to the affinity of each element. The atomic percentage is estimated according to XPS analysis and is presented for each individual element in Figure 6. Both metal Ta and Hf show a quick increase of nitridation followed by quasi-stable evolution when RN2=N2/(N2+Ar) increases from 0 to 50%. Al and Zr elements show a weak increase at RN2=5% and stabilization when RN2 continues to grow. However, Ti reveals a quasi-stable formation of nitride even though RN2 increases (Figure 6). The results demonstrate that all the elements are nitride during the deposition leading to the formation of high entropy nitride films.
Atomic percentage of individual elements, Al, Ti, Ta, Zr, and Hf as a function of nitrogen flow rate RN2=N2/(N2+Ar) during the preparation of AlTiTaZrHf(-N) HEFs. The curves are presented according to XPS analysis.
The mechanical properties have been investigated for large amounts of HEFs and the results revealed an improvement in the materials\' performances. Indeed, good hardness and wear resistance make the HEFs as well as their nitrides promising candidates for cutting tools for example. HEFs prepared by the magnetron sputtering technique showed that the mechanical properties are influenced by various deposition parameters. For example, Yu and co-workers [31] studied CrNbSiTiZr by changing the substrate bias voltage. The results showed that the hardness increased at a maximum of 12.4 ± 0.3 GPa with −50 V bias followed by a decrease to 9.8 ± 0.2 GPa when the bias is −200 V. Young’s modulus shows the same trend by increasing at 187.7 ± 3.3 GPa for −100 V and a decreasing to 162.3 ± 3.7 GPa for −200 V. The working pressure is also another parameter influencing the mechanical properties of HFEs. Kim and co-workers [32] reported high mechanical properties of AlCoCrNi films obtained with a pressure of 1.33 × 10−1 Pa. Indeed, at low pressure (1.33 Pa), the hardness is measured at 8.9 ± 0.9 GPa and the modulus at 142 ± 11 GPa. However, when the pressure reaches 1.33 × 10−1 Pa, the hardness increase to 16.8 ± 0.5 GPa and the modulus to 243 ± 39 GPa.
The nitrides show an increasing of mechanical properties as the nitrogen flow rate increases followed by a decrease as the flow continues to increase. This trend is seen for various high entropy nitrides [29, 41, 42, 43, 44]. An example is presented in Figure 7a. (AlCrMoTaTiZr)N HEFs, obtained with 40% nitrogen flow ratio, is the hardest film compared to others with a hardness of 40 GPa with Young’s modulus higher than 370 GPa. Residual stresses have been also studied and their evolution is depending on the nitrogen content. Zhang and co-workers [29] investigated the residual stress of (CrNbTiAlV)N HEFs at different nitrogen flows. The result is presented in Figure 7b. The metallic film has the lowest value of −2.35 GPa while a maximum (−6.55 GPa) is obtained for the nitride at 38 sccm.
Hardness (a) and Residual stress (b) of (CrNbTiAlV)Nx films deposited under different nitrogen flows. Figure reproduced with permission from [
In the case of oxides, as the oxygen flow rate increases the microstructure became dense and consequently the mechanical properties are improved. At a high flow rate, these properties degrade. The hardness of AlCoCrCu0.5FeNi reaches the maximum (11.3 ± 0.9 GPa) at 25% of O2 and decreases as the flow continues to increase.
Other results show that this trend is not always true. Khan and co-workers [45] reported no change in the mechanical properties by studying AlCoCrCu0.5FeNi films. These laters are prepared as a function of the working pressure. Their hardness was measured at 13 GPa while Young\'s modulus was evaluated at 204 GPa and no change was revealed as the pressure increased.
The change in microstructure could be the result of several factors such as preferential orientation and variation in crystallite size. These phenomena improve the tribological performance of HEFs. The presence of defects can also prevent plastic flow during deformation in the material that can change its hardness. The change in the hardness will lead to a change in its tribological properties.
The tribological performance of (AlCrNbSiTiMo)N has been studied by Lo and co-workers [46] at ambient temperature and after annealing at 700°C. The results showed a decrease in the friction coefficient, especially after annealing. This reduction difference in the coefficient of friction was measured at 0.2. At room temperature, the coefficient was 0.68 ± 0.09 while after annealing at 700°C it became 0.48 ± 0.08 as shown in Figure 8. The result revealed an improved wear resistance due to the formation of MoO3 after annealing, which acts as a lubricating effect.
Friction Coefficient of the AlCrNbSiTiMoN coatings. Figure reproduced with permission from [
By changing the content of the elements, the tribological properties can be improved. For example, the effect of Al was studied by Cui and co-workers [47] on FeCoCrNiMnAlx alloy. As the Al content increases, the friction coefficient of these films decreases. On the other hand, the incorporation of carbon, producing a lubricating effect can also reduce the friction coefficient [35].
Corrosion is described as a physical-chemical interaction between a metal and its environment leading to changes in its properties and significant degradation of its function. Developing corrosion-resistant materials is a necessary need to resolve the issue and improve their performance. Due to the elevated entropy, HEFs form solid solutions rather than intermetallic compounds. This makes the materials with best functional properties. The corrosion of HEFs has been mostly studied in nitric acid, salt (NaCl) and in HCl. It has been reported that Cr, Ni, Co and Ti elements can improve the corrosion resistance in acid solution. Mo element could inhibit pitting corrosion in a solution containing Cl. Such phenomena have been carried out for HEFs prepared by magnetron sputtering. The results revealed that these properties are influenced by different deposition parameters. To carry out the electrochemical measurements of the films, potentiodynamic polarization tests are used. The parameters include corrosion potential (Ecorr), pitting potential (Epit) and corrosion-current density (Icorr). This later can be used to estimate the corrosion rate as described by the equation below [48]:
Where ρ is the density of the alloys (g/cm3), Icorr (μA/cm2) and EW present the equivalent weight given by:
ni, fi and Wi are the ith elements, the masse fraction and the atomic weight of ith element in the alloy respectively.
Anti-corrosion performance of (CrNbTaTiW)C has been studied by Malinovskis and co-workers [19] in HCl solution with a concentration of 1M. The results revealed that the carbides showed the best corrosion resistance compared to that Stainless Steel. Gao and co-workers [49] performed a deposition of (CoCrFeNiAl0.3) on silicon by using magnetron sputtering. The films show better corrosion resistance compared to austenitic 304L stainless steel. Wang and a coworker [50] studied corrosion behavior of AlCoFeNiTiZr HEFs in NaCl solution. Three coatings, (Fe-Co-Ni)25(Al-Ti-Zr)75, (Fe-Co-Ni)20(Al-Ti-Zr)80, (Fe-Co-Ni)15(Al-Ti-Zr)85 have been tested. According to the reported results, (Fe-Co-Ni)25(Al-Ti-Zr)75 exhibits the lowest Icorr and the highest Ecorr revealing its best corrosion resistance compared to other films. Wang and co-worker [37] investigated the electrochemical properties of (CrNbSiTiZr)C in a 3.5 wt% NaCl solution. Figure 9 presented the potentiodynamic polarization curves of the film. The result is compared to that of 304L stainless steel (SS). The study reported that (CrNbSiTiZr)C shows a Ecorr of −189 mV and Icorr of 0.0026 μA/cm2. Ecorr is higher and Icorr is smaller than that of 304L SS (Ecorr= −319 mV; Icorr= 0.13 μA/cm2). Th result then reveal that (CrNbSiTiZr)C exhibits a higher corrosion resistance compared to that of 304L SS.
Potentiodynamic curve of (CrNbSiTiZr)C in 3.5 wt% NaCl solution. Figure reproduced with permission from [
The change in composition (variation in the elements contents) influences the microstructure. Therefore, the change of the microstructure will improve the functional properties such as corrosion resistance. Wang and co-workers [50] reported an improved corrosion resistance of (Fe-Co-Ni)x(Al-Ti-Zr)100-x as a result of the increase in Fe-Co-Ni content. As a result, (FeCoNi)25(AlTiZr)75 showed a better corrosion performance. The addition of Al in the refractory HEF films VNbMoTaW was beneficial in terms of increasing the corrosion resistance. With 2.37 at.% of Al present in the alloy, excellent corrosion resistance was measured compared to 304 stainless steels in 0.5M of H2SO4 [51]. However, increasing the Al content can have a negative effect on the quality of the film. Indeed, at high Al content porous oxides can be formed and the pores can easily facilitate the diffusion of acid. As a result, the corrosion resistance decreases.
Other deposition parameters strongly influence the anticorrosion performance of HEFs. Kao and co-workers [36] reported an improved corrosion resistance of CrNbSiTaZr films. The films were prepared in a C2H2 containing environment. Varying the bias voltage can also change the properties of the films. Von Fieandt and co-workers [52] showed a better corrosion resistance of (AlCrNbYZr)Nx films compared to stainless steel. The electrochemical measurements were done in HCl by changing the polarization voltage and the temperature.
Various HEFs have been prepared to investigate their high-temperature oxidation behavior. (Al0.34Cr0.22Nb0.11Si0.11Ti0.22)50N50 HEFs have been annealed at 900°C for 50 hours [17]. Two different oxides were formed: α-Al2O3 and rutile-TiO2. The dense Al2O3 formed on the top layer of the films was a key reason to improve their oxidation resistance. Compared to traditional films TiN and TiAlN prepared under the same conditions, (Al0.34Cr0.22Nb0.11Si0.11Ti0.22)50N50 HEFs reveal the best oxidation resistance and can be potential candidates for developing high-temperature applications. The element content is one of the influencing parameters that can improve the oxidation resistance of the films. Indeed, Al and Si can lead to the formation of dense α-Al2O3 and α-SiO2 layers on HEFs at high temperature which improves their oxidation resistance. The oxidation behavior of (AlCrNbTaTi)N films, in air as a function of Si concentration, was reported by Kretschmer and co-workers [18]. The films were annealed at 850°C for 100 hours. Without Si, the oxide thickness of the film is important (2700 nm), however when Si was added the oxide thickness was measured at 280 nm. This means that Si forms a dense layer on the surface during the oxidation preventing then the diffusion of the oxygen in the film.
Tsai and co-workers [53] reported the same trend of Si effect. Figure 10 shows the variation of the oxide thickness formed according to Si content in the films. As Si content increases, the thickness of oxide layer decreases revealing a good oxidation resistance at high temperature.
Cross-sectional SEM micrographs of the (AlCrMoTaTi)N HEFs with (a) 0 at.%, (b) 2.77 at.%, and (c) 7.51 at.% of Si coatings after annealing at different temperature in air. Figure reproduced with permission from [
In the case of HfNbTaTiZr film HEFs, it was shown that oxygen reacted with all elements forming oxide nanoclusters. XPS was used to analyze the oxidation behavior and the results revealed 66 at.% of oxygen content where no oxide was determined by other techniques like SEM, TEM and X-ray diffraction [54]. The oxygen was found to preferentially bind to Ti, Zr and Hf rather than other elements.
HEFs deposited by magnetron sputtering techniques have been exploited to develop some applications. They can serve as surface protective materials. Among the different applications, materials for biomedical and for machining will be presented in this section.
Various scientific research has been focused on coatings to improve the performance of implants and prostheses. Compared to traditional coatings using this field, HEFs become the hot spot in surface engineering development. Two films, (HfNbTaTiZr)N and (HfNbTaTiZr)C, have been prepared by magnetron sputtering technique [55]. The corrosion property of these films was simulated in body fluid. The results have revealed a very small ratio of dead cells that were observed for both (HfNbTaTiZr)N and (HfNbTaTiZr)C HEFs. Si was used to improve the biocompatibility of the materials. Valdescu and co-workers [11] have replaced Ta with Si in the case of (TiZrNbTaHf)C. Considering the role of electrostatic interactions between the biomaterial surface and the cells, the authors examined the effects of surface charge (characterized by electrical potential and work function) on the biocompatibility property. A low electrical potential and high work function of (TiZrNbSiHf)C film was obtained revealing that this film exhibits best biocompatibility.
The dry machining process is seen as the best alternative to replace the oils in the industry. Because the oils have a negative impact on both operator health and the ecology. An environmental transition is, therefore, necessary to develop clean processes. HEFs are now interesting materials where scientific efforts are underway to improve the performance of cutting tools. thermal and machining properties of (Al0.34Cr0.22Nb0.11Si0.11Ti0.22)50N50 HEF, have been examined by Shen and co-workers [56]. The cutting performances of the films are better as the milling was operating at a high temperature. Due to its superior properties like high hardness, good thermal stability and outstanding oxidation resistance, the HEF shows great potential to be exploited in machining applications. The study reported that, after 900 m of cutting, the wear depth is 226, 202, 184, and 175 μm for uncoated, TiN, TiAlN and (Al0.34Cr0.22Nb0.11Si0.11Ti0.22)50N50 HEF respectively.
The chapter reports and discusses briefly various properties of HEFs fabricated by magnetron sputtering. Intensive scientific efforts have been paid to this area for improving the materials surfaces and developing innovant materials. The preparation of the films is performed according to various deposition parameters.
Two processes are reported, standard direct current magnetron sputtering (DCMS) and high power impulse magnetron sputtering (HiPIMS) that are used to prepare HEFs in different environments. HiPIMS process led to the formation of denser microstructure compared to that with DCMS. Substrate bias voltage, working pressure, gas flow rate as deposition parameters, all are discussed and revealed that they strongly influence the physico-chemical properties of HEFs. Amorphous to crystalline structure of the most prepared HEFs transition took place upon introduction of gas like N2 or CH4 or O2.
Two functional properties, electrochemical (corrosion) and physical (oxidation) are reported and discussed. Th both properties have been reported to be influenced by different deposition parameters. The preparation of dense films prevents acid attack and improve corrosion resistance. The formation of some oxide layers such as α-Al2O3 and α-SiO2 on the top film surface plays a great role in protecting the materials from oxidation at high temperature.
Some HEFs are exploited to develop application in the various materials field. Examples are reported on biomaterials and machining processes showing the best performances of the films compared to traditional coatings.
The prepared HEFs revealed enhanced surface protection ability. Even with the promising performances that possess the HEFs, more efforts are needed to develop a deep understanding of this class of materials. The complexity of the materials increases with the number of possible combinations of elements. Traditional metallurgy cannot meet the requirements of quick results, which requires a lot of time depending on the combinations. Advanced characterization techniques are needed which must be combined with theoretical simulation to solve this type of problem. Artificial intelligence can also be added to the knowledge of traditional metallurgy to define new approaches for studying innovative HEFs.
Authors ME, FS and FSC thank the Université de Technologie de Troyes (UTT) and Commissariat à l\'Energie Atomique et aux énergies alternatives (CEA) Saclay.
The authors declare no conflict of interest.
IntechOpen aims to guarantee that original material is published while at the same time giving significant freedom to our Authors. We uphold a flexible Copyright Policy, guaranteeing that there is no transfer of copyright to the publisher and Authors retain exclusive copyright to their Work.
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\\n\\nCORRESPONDING AUTHOR'S GRANT OF RIGHTS
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\\n\\nSubject to the license granted above, the Author and Co-Authors retain patent, trademark and other intellectual property rights to the Work.
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\\n\\nAUTHOR'S DUTIES
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\\n\\nThe Author shall obtain written informed consent for publication from those who might recognize themselves or be identified by others, for example from case reports or photographs.
\\n\\nThe Author shall respect confidentiality during and after the termination of this Agreement. The information contained in all correspondence and documents as part of the publishing activity between IntechOpen and the Author and Co-Authors are confidential and are intended only for the recipients. The contents of any communication may not be disclosed publicly and are not intended for unauthorized use or distribution. Any use, disclosure, copying, or distribution is prohibited and may be unlawful.
\\n\\nAUTHOR'S WARRANTY
\\n\\nThe Author and Co-Authors confirm and warrant that the Work does not and will not breach any applicable law or the rights of any third party and, specifically, that the Work contains no matter that is defamatory or that infringes any literary or proprietary rights, intellectual property rights, or any rights of privacy.
\\n\\nThe Author and Co-Authors confirm that: (i) the Work is their original work and is not copied wholly or substantially from any other work or material or any other source; (ii) the Work has not been formally published in any other peer-reviewed journal or in a book or edited collection, and is not under consideration for any such publication; (iii) Authors and any applicable Co-Authors are qualifying persons under section 154 of the Copyright, Designs and Patents Act 1988; (iv) Authors and any applicable Co-Authors have not assigned, and will not during the term of this Publication Agreement purport to assign, any of the rights granted to IntechOpen under this Publication Agreement; and (v) the rights granted by this Publication Agreement are free from any security interest, option, mortgage, charge or lien.
\\n\\nThe Author and Co-Authors also confirm and warrant that: (i) he/she has the power to enter into this Publication Agreement on his or her own behalf and on behalf of each Co-Author; and (ii) has the necessary rights and/or title in and to the Work to grant IntechOpen, on behalf of themselves and any Co-Author, the rights and licences in this Publication Agreement. If the Work was prepared jointly by the Author and Co-Authors, the Author confirms that: (i) all Co-Authors agree to the submission, license and publication of the Work on the terms of this Publication Agreement; and (ii) the Author has the authority to enter into this biding Publication Agreement on behalf of each Co-Author. The Author shall: (i) ensure each Co-Author complies with all relevant provisions of this Publication Agreement, including those relating to confidentiality, performance and standards, as if a party to this Publication Agreement; and (ii) remain primarily liable for all acts and/or omissions of each Co-Author.
\\n\\nThe Author agrees to indemnify IntechOpen harmless against all liabilities, costs, expenses, damages and losses, as well as all reasonable legal costs and expenses suffered or incurred by IntechOpen arising out of, or in connection with, any breach of the agreed confirmations and warranties. This indemnity shall not apply in a situation in which a claim results from IntechOpen's negligence or willful misconduct.
\\n\\nNothing in this Publication Agreement shall have the effect of excluding or limiting any liability for death or personal injury caused by negligence or any other liability that cannot be excluded or limited by applicable law.
\\n\\nTERMINATION
\\n\\nIntechOpen has the right to terminate this Publication Agreement for quality, program, technical or other reasons with immediate effect, including without limitation (i) if the Author and/or any Co-Author commits a material breach of this Publication Agreement; (ii) if the Author and/or any Co-Author (being a private individual) is the subject of a bankruptcy petition, application or order; or (iii) if the Author and/or any Co-Author (as a corporate entity) commences negotiations with all or any class of its creditors with a view to rescheduling any of its debts, or makes a proposal for, or enters into, any compromise or arrangement with any of its creditors.
\\n\\nIn the event of termination, IntechOpen will notify the Author of the decision in writing.
\\n\\nIntechOpen’s DUTIES AND RIGHTS
\\n\\nUnless prevented from doing so by events beyond its reasonable control, IntechOpen, at its discretion, agrees to publish the Work attributing it to the Author and Co-Authors.
\\n\\nUnless prevented from doing so by events beyond its reasonable control, IntechOpen agrees to provide publishing services which include: managing editing (editorial and publishing process coordination, Author assistance); publishing software technology; language copyediting; typesetting; online publishing; hosting and web management; and abstracting and indexing services.
\\n\\nIntechOpen agrees to offer free online access to readers and use reasonable efforts to promote the Publication to relevant audiences.
\\n\\nIntechOpen is granted the authority to enforce the rights from this Publication Agreement on behalf of the Author and Co-Authors against third parties, for example in cases of plagiarism or copyright infringements. In respect of any such infringement or suspected infringement of the copyright in the Work, IntechOpen shall have absolute discretion in addressing any such infringement that is likely to affect IntechOpen's rights under this Publication Agreement, including issuing and conducting proceedings against the suspected infringer.
\\n\\nIntechOpen has the right to include/use the Author and Co-Authors names and likeness in connection with scientific dissemination, retrieval, archiving, web hosting and promotion and marketing of the Work and has the right to contact the Author and Co-Authors until the Work is publicly available on any platform owned and/or operated by IntechOpen.
\\n\\nMISCELLANEOUS
\\n\\nFurther Assurance: The Author shall ensure that any relevant third party, including any Co-Author, shall execute and deliver whatever further documents or deeds and perform such acts as IntechOpen reasonably requires from time to time for the purpose of giving IntechOpen the full benefit of the provisions of this Publication Agreement.
\\n\\nThird Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
\\n\\nEntire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by, or on behalf of, the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (known as the "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of any fraudulent pre-contract misrepresentation or concealment.
\\n\\nWaiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
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\\n\\nNo partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Author or any Co-Author, nor authorize any party to make or enter into any commitments for, or on behalf of, any other party.
\\n\\nGoverning law: This Publication Agreement and any dispute or claim, including non-contractual disputes or claims arising out of, or in connection with it, or its subject matter or formation, shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of, or in connection with, this Publication Agreement, including any non-contractual disputes or claims.
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\n\nThe foregoing licenses shall survive the expiry or termination of this Publication Agreement for any reason.
\n\nThe Author, on his or her own behalf and on behalf of any of the Co-Authors, reserves the following rights in the Work but agrees not to exercise them in such a way as to adversely affect IntechOpen's ability to utilize the full benefit of this Publication Agreement: (i) reprographic rights worldwide, other than those which subsist in the typographical arrangement of the Work as published by IntechOpen; and (ii) public lending rights arising under the Public Lending Right Act 1979, as amended from time to time, and any similar rights arising in any part of the world.
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\n\nSubject to the license granted above, copyright in the Work and all versions of it created during IntechOpen's editing process, including all published versions, is retained by the Author and any Co-Authors.
\n\nSubject to the license granted above, the Author and Co-Authors retain patent, trademark and other intellectual property rights to the Work.
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\n\nAUTHOR'S DUTIES
\n\nWhen distributing or re-publishing the Work, the Author agrees to credit the Monograph/Compacts as the source of first publication, as well as IntechOpen. The Author guarantees that Co-Authors will also credit the Monograph/Compacts as the source of first publication, as well as IntechOpen, when they are distributing or re-publishing the Work.
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\n\nAll payments shall be due 30 days from the date of issue of the invoice. The Author or whoever is paying on behalf of the Author and Co-Authors will bear all banking and similar charges incurred.
\n\nThe Author shall obtain in writing all consents necessary for the reproduction of any material in which a third-party right exists, including quotations, photographs and illustrations, in all editions of the Work worldwide for the full term of the above licenses, and shall provide to IntechOpen, at its request, the original copies of such consents for inspection or the photocopies of such consents.
\n\nThe Author shall obtain written informed consent for publication from those who might recognize themselves or be identified by others, for example from case reports or photographs.
\n\nThe Author shall respect confidentiality during and after the termination of this Agreement. The information contained in all correspondence and documents as part of the publishing activity between IntechOpen and the Author and Co-Authors are confidential and are intended only for the recipients. The contents of any communication may not be disclosed publicly and are not intended for unauthorized use or distribution. Any use, disclosure, copying, or distribution is prohibited and may be unlawful.
\n\nAUTHOR'S WARRANTY
\n\nThe Author and Co-Authors confirm and warrant that the Work does not and will not breach any applicable law or the rights of any third party and, specifically, that the Work contains no matter that is defamatory or that infringes any literary or proprietary rights, intellectual property rights, or any rights of privacy.
\n\nThe Author and Co-Authors confirm that: (i) the Work is their original work and is not copied wholly or substantially from any other work or material or any other source; (ii) the Work has not been formally published in any other peer-reviewed journal or in a book or edited collection, and is not under consideration for any such publication; (iii) Authors and any applicable Co-Authors are qualifying persons under section 154 of the Copyright, Designs and Patents Act 1988; (iv) Authors and any applicable Co-Authors have not assigned, and will not during the term of this Publication Agreement purport to assign, any of the rights granted to IntechOpen under this Publication Agreement; and (v) the rights granted by this Publication Agreement are free from any security interest, option, mortgage, charge or lien.
\n\nThe Author and Co-Authors also confirm and warrant that: (i) he/she has the power to enter into this Publication Agreement on his or her own behalf and on behalf of each Co-Author; and (ii) has the necessary rights and/or title in and to the Work to grant IntechOpen, on behalf of themselves and any Co-Author, the rights and licences in this Publication Agreement. If the Work was prepared jointly by the Author and Co-Authors, the Author confirms that: (i) all Co-Authors agree to the submission, license and publication of the Work on the terms of this Publication Agreement; and (ii) the Author has the authority to enter into this biding Publication Agreement on behalf of each Co-Author. The Author shall: (i) ensure each Co-Author complies with all relevant provisions of this Publication Agreement, including those relating to confidentiality, performance and standards, as if a party to this Publication Agreement; and (ii) remain primarily liable for all acts and/or omissions of each Co-Author.
\n\nThe Author agrees to indemnify IntechOpen harmless against all liabilities, costs, expenses, damages and losses, as well as all reasonable legal costs and expenses suffered or incurred by IntechOpen arising out of, or in connection with, any breach of the agreed confirmations and warranties. This indemnity shall not apply in a situation in which a claim results from IntechOpen's negligence or willful misconduct.
\n\nNothing in this Publication Agreement shall have the effect of excluding or limiting any liability for death or personal injury caused by negligence or any other liability that cannot be excluded or limited by applicable law.
\n\nTERMINATION
\n\nIntechOpen has the right to terminate this Publication Agreement for quality, program, technical or other reasons with immediate effect, including without limitation (i) if the Author and/or any Co-Author commits a material breach of this Publication Agreement; (ii) if the Author and/or any Co-Author (being a private individual) is the subject of a bankruptcy petition, application or order; or (iii) if the Author and/or any Co-Author (as a corporate entity) commences negotiations with all or any class of its creditors with a view to rescheduling any of its debts, or makes a proposal for, or enters into, any compromise or arrangement with any of its creditors.
\n\nIn the event of termination, IntechOpen will notify the Author of the decision in writing.
\n\nIntechOpen’s DUTIES AND RIGHTS
\n\nUnless prevented from doing so by events beyond its reasonable control, IntechOpen, at its discretion, agrees to publish the Work attributing it to the Author and Co-Authors.
\n\nUnless prevented from doing so by events beyond its reasonable control, IntechOpen agrees to provide publishing services which include: managing editing (editorial and publishing process coordination, Author assistance); publishing software technology; language copyediting; typesetting; online publishing; hosting and web management; and abstracting and indexing services.
\n\nIntechOpen agrees to offer free online access to readers and use reasonable efforts to promote the Publication to relevant audiences.
\n\nIntechOpen is granted the authority to enforce the rights from this Publication Agreement on behalf of the Author and Co-Authors against third parties, for example in cases of plagiarism or copyright infringements. In respect of any such infringement or suspected infringement of the copyright in the Work, IntechOpen shall have absolute discretion in addressing any such infringement that is likely to affect IntechOpen's rights under this Publication Agreement, including issuing and conducting proceedings against the suspected infringer.
\n\nIntechOpen has the right to include/use the Author and Co-Authors names and likeness in connection with scientific dissemination, retrieval, archiving, web hosting and promotion and marketing of the Work and has the right to contact the Author and Co-Authors until the Work is publicly available on any platform owned and/or operated by IntechOpen.
\n\nMISCELLANEOUS
\n\nFurther Assurance: The Author shall ensure that any relevant third party, including any Co-Author, shall execute and deliver whatever further documents or deeds and perform such acts as IntechOpen reasonably requires from time to time for the purpose of giving IntechOpen the full benefit of the provisions of this Publication Agreement.
\n\nThird Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
\n\nEntire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by, or on behalf of, the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (known as the "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of any fraudulent pre-contract misrepresentation or concealment.
\n\nWaiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
\n\nVariation: No variation of this Publication Agreement shall have effect unless it is in writing and signed by the parties, or their duly authorized representatives.
\n\nSeverance: If any provision, or part-provision, of this Publication Agreement is, or becomes invalid, illegal or unenforceable, it shall be deemed modified to the minimum extent necessary to make it valid, legal and enforceable. If such modification is not possible, the relevant provision or part-provision shall be deemed deleted. Any modification to, or deletion of, a provision or part-provision under this clause shall not affect the validity and enforceability of the rest of this Publication Agreement.
\n\nNo partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Author or any Co-Author, nor authorize any party to make or enter into any commitments for, or on behalf of, any other party.
\n\nGoverning law: This Publication Agreement and any dispute or claim, including non-contractual disputes or claims arising out of, or in connection with it, or its subject matter or formation, shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of, or in connection with, this Publication Agreement, including any non-contractual disputes or claims.
\n\nPolicy last updated: 2018-09-11
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On September, 29th 2006 he has won a post PhD fellowship from the university of Bologna (from October 2006 to October 2008), at the competitive examination he was ranked first in the industrial engineering area. He extensively served as referee for several international journals. He is author/coauthor of more than 100 research papers. He has been involved in some projects supported by MURST and European Community. 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Delac received his B.Sc.E.E. degree in 2003 and is currentlypursuing a Ph.D. degree at the University of Zagreb, Faculty of Electrical Engineering andComputing. His current research interests are digital image analysis, pattern recognition andbiometrics.",institutionString:null,institution:{name:"University of Zagreb",country:{name:"Croatia"}}},{id:"557",title:"Dr.",name:"Andon",middleName:"Venelinov",surname:"Topalov",slug:"andon-topalov",fullName:"Andon Topalov",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/557/images/1927_n.jpg",biography:"Dr. Andon V. Topalov received the MSc degree in Control Engineering from the Faculty of Information Systems, Technologies, and Automation at Moscow State University of Civil Engineering (MGGU) in 1979. He then received his PhD degree in Control Engineering from the Department of Automation and Remote Control at Moscow State Mining University (MGSU), Moscow, in 1984. From 1985 to 1986, he was a Research Fellow in the Research Institute for Electronic Equipment, ZZU AD, Plovdiv, Bulgaria. In 1986, he joined the Department of Control Systems, Technical University of Sofia at the Plovdiv campus, where he is presently a Full Professor. He has held long-term visiting Professor/Scholar positions at various institutions in South Korea, Turkey, Mexico, Greece, Belgium, UK, and Germany. And he has coauthored one book and authored or coauthored more than 80 research papers in conference proceedings and journals. 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