Kinetic parameters of hydrogen reduction reaction in a 1 mol L−1 KОН.
\\n\\n
More than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\\n\\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\\n\\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\\n\\nAdditionally, each book published by IntechOpen contains original content and research findings.
\\n\\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\\n\\n\\n\\n
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'
Simba Information has released its Open Access Book Publishing 2020 - 2024 report and has again identified IntechOpen as the world’s largest Open Access book publisher by title count.
\n\nSimba Information is a leading provider for market intelligence and forecasts in the media and publishing industry. The report, published every year, provides an overview and financial outlook for the global professional e-book publishing market.
\n\nIntechOpen, De Gruyter, and Frontiers are the largest OA book publishers by title count, with IntechOpen coming in at first place with 5,101 OA books published, a good 1,782 titles ahead of the nearest competitor.
\n\nSince the first Open Access Book Publishing report published in 2016, IntechOpen has held the top stop each year.
\n\n\n\nMore than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\n\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\n\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\n\nAdditionally, each book published by IntechOpen contains original content and research findings.
\n\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\n\n\n\n
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The laparoscopic technique has been enthusiastically applied to the resection of colorectal cancer for more than 15 years [1]. There is evidence that laparoscopy for colorectal cancer offers the opportunity for a meticulous dissection of the mesocolon and mesorectum under direct vision while facilitating a true no-touch technique [2]. Additional benefits, such as less postoperative pain, reduced need for postoperative analgesia, less ileus, shorter hospital stay, less blood loss, and better cosmesis are also well documented [3,4].
During recent years, great effort has been made to minimize parietal trauma for cosmetic reasons and to further reduce surgery-related pain and morbidity. New techniques, such as natural orifice transluminal endoscopic surgery (NOTES) [5] have been developed in order to reach the goal of “scarless” surgery. Although NOTES actually allows for no scarring of the body surface, it has several disadvantages and limitations with the currently available instruments, including limited access, less familiar working angles and operative approaches. Furthermore, it is associated with possible complications caused by opening of the stomach, colon or vagina, and may not be fully suitable or safe for advanced procedures, such as colectomies [6].
Single incision laparoscopic surgery (SILS) is currently regarded as the next major advance in minimally invasive surgical approaches to colorectal disease that is more feasible for generalized use [7-10]. SILS reduces the invasiveness of laparoscopic conventional surgery (LCS) by decreasing the number of incisions and ports through the abdominal wall. This theoretically could provide important clinical advantages, including less postoperative pain, reduction of port-site associated morbidity (such as wound infection, bleeding, visceral injury and port site herniation), quicker recovery and shorter hospital stay. The small incision through the abdominal wall allows for “scarless” surgery as the wound is usually hidden within the umbilicus, thus providing potentially better cosmesis. Moreover, SILS permits surgeons to use familiar standard laparoscopic instruments but also perform complex procedures, such as colorectal operations, which require extraction of large surgical specimens or intestinal anastomosis.
SILS was first reported in 1992 by gynecologists who performed single-incision hysterectomy [11]. The performance of the first transumbilical cholecystectomy was published in 1999 [12] and the first single-incision appendectomy was reported in 1998 [13]. The use of SILS in colorectal surgery was first reported in 2008 by Remzi and co-workers [8] and Bucher and colleagues [14].
Since these first reports, it has been evident that SILS raises a number of specific new challenges compared with LCS. The skills required for SILS are different from those needed in conventional multiport laparoscopy, even for experienced laparoscopic surgeons [15]. The handling of straight instruments in parallel with the laparoscope through a small single incision decreases the freedom of movement for the surgeon, and complicates the holding of the laparoscope for the assistant and instruments for the surgeon. The most outstanding technical challenges involved in SILS are the following:
Loss of triangulation with straight instruments: the loss of this dogmatic principle of laparoscopic surgery often imposes the need to operate with crossed hands and does not allow an ergonomically favorable position for the surgeon and assistants. The inherent technical challenge is that the visual axis becomes more axial or in-line, so a movement of the camera often results in a inadvertent movement of an adjacent instrument, thus increasing the difficulty of performing even relatively simple tasks.
Restricted number of working instruments and thus difficulty of achieving correct exposure and the necessary traction to tissues.
Restricted external working space: the multiple instruments and laparoscopes required for a procedure are competing for the same space at the fulcrum of the entry port, causing external hand collisions and difficulty with instrument tip manipulation internally.
Difficulty in maintaining pneumoperitoneum.
Requirement of training and adjustment.
New operative hardware is being developed to facilitate the technique [16]. Many of the big healthcare manufacturers have developed multilumen access devices to allow for the insertion of several instruments through a single large fascial incision (Figure 1).
Single port systems: (a) Uni-x (Pnavel Systems, Morganville, New Jersey, USA); (b) X-Cone (Karl Storz, Tuttlingen, Germany); (c) Endo-Cone (Karl Storz, Tuttlingen, Germany); (d) SILS Port (Covidien, Norwalk, Connecticut, USA); (e) Olympus TriPort + (Advanced Surgical Concepts, Bray, Ireland.
Initially, these devices offered three openings with limited gas inflow and outflow, but we are now seeing revision of the devices, incorporating more access ports so standard laparoscopic dissection techniques can be utilized. Newly designed equipment, such as articulating or curved instruments and flexible scopes, have been introduced to recreate triangulation (Figure 2).
Articulating and curved instruments for SILS: (a) SILS Hand Instrument (Covidien, Norwalk, Connecticut, USA); (b) The Cuschieri Coaxial Deviating Instruments (Karl Storz, Tuttlingen, Germany); (c) Cambridge Endo Instruments (Cambridge Endoscopic Devices, Framingham, Massachusetts, USA).
Moreover, the introduction of an extra-long, 5 mm laparoscope allows placement of the camera on a different plane from the other instruments and help in moving the operator’s hand further apart to avoid handle collision (Figure 3) [17]. All these devices have made single site surgery easier and more efficient.
Extra-long, 5 mm, 30° laparoscope (Karl Storz, Tuttlingen, Germany).
All the challenges encountered with single-port surgery are magnified with colorectal procedures. Unlike laparoscopic cholecystectomy or appendicectomy, which involve surgery in only one abdominal quadrant, single-incision laparoscopic colectomy often requires operating in different abdominal quadrants. In addition, the need for adequate oncological margins and the creation of a tension-free anastomosis are essential. Although the use of this new approach for complex colorectal procedures might understandingly be viewed as difficult to implement, over the past few years there has been significant interest in SILS for colonic resections in both benign and malignant conditions. In fact, between 2008 and 2012, a nearly 7-fold increase occurred in the number of articles related to single-port colorectal surgery [18-20]. Unfortunately, the currently available literature relating to the technique includes mostly case reports or small case series describing the feasibility, safety and technical difficulties of different operations [21-42]. There are very few studies comparing SILS to LCS and there is a need for randomized controlled trials to definitively establish that SILS is no different from standard laparoscopic surgery in terms of completion rates, complications and oncological adequacy but with the advantage of being more cosmetic with subsequently reduced morbidities including pain [43]. The studies published to date have a number of other flaws limiting their impact. These include low sample size, selection bias and difficulty in blinding the patients enrolled. The vast majority of studies involve a very carefully selected SILS cohort of uncomplicated cases, which significantly limits their generalization.
The most significant datum emerging from the literature is that colonic SILS has been offered to date to a highly selected group of patients [18,19]. This selection is based on two main parameters: body mass index (BMI) that is an indirect measure of visceral fat, and tumor site, that is directly linked to the type of surgical procedure.
It is well known that visceral fat is one the most critical factors in the identification of the correct surgical plane in laparoscopic surgery [44]. This concept is obviously amplified in SILS and visceral obesity is reported as the primary cause of conversion to multiport laparoscopy in most studies [45]. Therefore it is understandable that most patients who are candidates for this type of surgery had a low BMI. Makino et al. [18] have reviewed 23 studies with a total of 378 patients undergoing single-port colectomy. The mean value of BMI was 25.5 kg/m2 in these patients. Similar results have been found by Fung et al. [19] in their recent review. These authors have analyzed 38 colonic SILS articles containing 565 patients and the median BMI was 25.8 kg/m2. On the basis of these findings, some studies have suggested the use of preoperative abdominal computed tomography to predict accurately the pattern of visceral fat, allowing better selection of patients for SILS colectomy and reducing the number of conversions [44].
The other factor that has markedly influenced the currently available data on SILS for colorectal cancer is the type of surgical procedure. Makino et al. [18] have reported that 279 (73.8%) of the 378 procedures analyzed in their review were right hemicolectomy, followed by sigmoidectomy (n = 27), performed essentially for diverticular disease, and anterior resection of the rectum (n = 20). Moreover, a high number of published studies have specifically limited the analysis of safety, feasibility and short-term results to only single-port right hemicolectomy [14,25,32-38,42,45-48], thus demonstrating that this type of procedure is the least complex to perform with the single-port technique at the beginning of the experience. Actually, right hemicolectomy involves surgery only in one/two quadrants while left procedures require operating in a multitude of different and opposite abdominal quadrants, from the hypochondrium for splenic flexure mobilization to the pelvis for a total mesorectal excision (TME). Moreover, in right hemicolectomy the surgeon has the possibility of creating an extracorporeal intestinal anastomosis through umbilical access while in left colectomies and anterior resection of the rectum the anastomosis is intracorporeal, thus augmenting the complexity of the procedure.
These considerations clearly show that there is an inevitable case-selection bias in assessing the outcomes of colo-rectal SILS from published studies. Although randomized controlled trials comparing single-port and multi-port right hemicolectomy have not been reported yet, the most significant data available to date relate to this type of procedure. In 2012, the two largest experiences with single-port right hemicolectomies in a single institution have been reported. Waters et al. [49] analyzed the short-term outcomes with single-incision right hemicolectomy in 100 patients. Operative indications were oncological in 92 patients, 57 for adenocarcinoma and 35 for polyps not suitable for endoscopic removal. Morbidity (13%) and mortality (1%) rates were acceptable as well as operative time (median value, 105 minutes) and conversion rate to multiport or open procedures (2% and 4%, respectively). Most importantly, there was no compromise of oncological adequacy with no positive tumor margins and a mean number of 18 lymph nodes retrieved and examined in the surgical specimens. Interestingly, patients with a wide range of BMI measurements were offered single-incision right hemicolectomy, with the largest approaching superobesity at a BMI of 46 kg/m2 and a mean patient BMI of 28. Unfortunately, no results regarding postoperative pain, cosmetic results or direct comparison with the multi-port laparoscopic approach were reported.
Chew et al. [50] have reported the short outcomes of single-incision laparoscopic hemicolectomy in 40 consecutive patients. These results were compared with those of 104 conventional laparoscopic hemicolectomies. Indications for surgery were oncological in the majority of patients in the two groups. The authors found that single-incision right hemicolectomy is a feasible and safe procedure with equivalent outcomes in terms of operative time, oncological adequacy, postoperative morbidity, and conversions when compared with conventional laparoscopic right hemicolectomy. In particular, there were no differences in lymph node retrieval (median value of 18 and 19 lymph nodes for multi-port and single-port surgery, respectively) and resection margin clearance.
The data regarding left sided procedures, in particular anterior resection of the rectum for cancer, are much more limited. This is mainly due to the complexity of these procedures, in particular some surgical steps such as mobilizing the splenic flexure and dissection of the mesorectum. The fairly great distance of the spleen and the deep pelvis from the umbilicus amplify the difficulty of creating instrument triangulation, especially when standard, straight laparoscopic instruments are used. Even adequate traction of the rectum and stapling procedures have been associated with technical difficulties and adjunctive methods of traction and suspension such as transparietal suture, are frequently needed to achieve adequate surgical exposure [51-56]. Bulut et al. [57] have recently reported their early experience in single-incision surgery for rectal cancer treatment. This study was conducted on 10, highly selected patients: the mean tumor diameter was very small (3.2 cm), BMI was ≤25 in all patients and 8 of them were females, thus providing the advantages of a wide pelvis and relative lack of visceral fat. Although the authors stated that single-incision surgery for rectal cancer can be performed safely in this kind of patient, the overall mean operation time was quite long (240 min) and 6 patients received stomas (4 had diverting ileostomy after anterior resection of the rectum and 2 had colostomy after Hartmann procedure and abdominoperineal resection). Moreover, mesorectum excision was classified as nearly complete in 4 patients and the median number of examined lymph nodes was quite low, namely 14.
One of the most challenging maneuvers in single-incision rectal surgery is maintaining an adequate operative field during TME. Uematsu et al. [54] have proposed a new rectum-suspending system composed of a suspending bar and a bowel clamp with an extracorporeal magnetic tool. This apparatus, along with single access through the right iliac fossa instead of the umbilicus, allowed the authors to perform TME and transect the rectum by ensuring a proper tension. Nevertheless, the proposed new technique is actually complex and, as the authors stated, is not recommended for males with narrow pelvis or obese individuals or when mobilization of the splenic flexure is required because of the distance between the spleen and the single access through the right iliac fossa. Altogether, these data clearly show that some unresolved issues still remain in performing SILS for the treatment of rectal cancer.
There are more data, which are somewhat more reliable regarding other less complex left-sided procedures, such as left hemicolectomy or sigmoidectomy [52,58-60]. In fact, sigmoidectomy is the most frequent procedure performed for benign left-side pathology, predominantly diverticular disease or large colonic polyps not suitable for endoscopic removal. Recently, Vestweber et al. [61] have reported the largest series of patients undergoing single-incision colorectal surgery in a single institution. One hundred and fifty out of 244 procedures were sigmoidectmy (n = 145) with left hemicolectomies (n = 4) and high anterior resection of the rectum (n = 1). Most of these patients were operated on for diverticular disease (n = 142) followed by colonic polyps (n = 4) and colonic cancer (n = 4). The mean operative time for left-sided procedures was 146 ± 48 min and in all cases standard straight, non-articulating laparoscopic instruments along with ultrasonic or radiofrequency dissector/sealer were used. It seems that the authors did not experience any particular technical problems in performing these types of procedures that do not actually need wide splenic flexure mobilization or mesorectal dissection. The fairly higher incidence of early postoperative complications (12.6%) than rates stated in the literature, was imputed to the high rate of severe, complicated diverticular disease rather than to the complexity of single-incision procedure.
The literature concerning subtotal colectomy or proctocolectomy (with or without ileoanal anastomosis), at this time consists only of case reports and a few small case series [62-68]. The predominant indication for this type of operation has been ulcerative colitis followed by polyposis coli [64,65,67]. Overall, 36 single-incision total colectomies have been reported in the literature: these studies have demonstrated the feasibility and safety of single-incision technique even in these more complex colonic procedures but cannot provide any comparative results with traditional laparoscopy. It is likely that cosmetic results will be magnified by single-incision total colectomy since patients suffering from ulcerative colitis or polyposis coli are usually young and may prefer a small incision hidden in the umbilicus. If an ileostomy is scheduled, the single incision is usually performed in the right lower quadrant of the abdomen and the terminal ileum is brought out through this port-site, thus minimizing the traumatic and cosmetic impact of the procedure.
As all these data indicate, there are still several limitations to an analysis of the adequacy of single-incision technique in the treatment of colorectal cancer. The most important limiting factor in the interpretation of reported outcomes is the careful selection of patients, with an almost 3-fold predominance of right-sided pathology, a low to average BMI and non-bulky colonic disease. If this case-selection bias is taken into account and the oncological adequacy of a single-incision procedure is hypothetically accepted, this innovation would be justified only in the presence of clear short-term benefits over conventional laparoscopic colonic surgery. These benefits should comprise a lower complication rate, reduced postoperative pain, faster recovery and better cosmesis.
To date, only two randomized trials have compared short-term outcomes after single-incision and conventional laparoscopic colectomies for colon cancer. In 2011, Huscher et al. [69] reported the results of a study conducted on 32 patients, with 16 in the single-incision and 16 in the conventional laparoscopic group. Although the authors confirmed the safety and technical feasibility of single-incision colectomy, they did not show any superiority of the procedure over conventional laparoscopy in terms of postoperative morbidity, resumption of oral liquid/solid food intake and length of hospital stay.
More recently, Poon et al. [70] reported findings from a randomized controlled trial, which enrolled 50 patients, 25 in each study group. As expected, the patients were carefully selected in regard to BMI (median value, 23.2 kg/m2) and tumor size (< 4 cm). On the contrary, there was a predominance of left-sided procedures, with 14 anterior resections, 1 sigmoidectomy, 2 left hemicolectomies and only 8 right hemicolectomies in the single-incision group. The authors did not find any statistically significant difference in operative outcome and oncological adequacy between the single-incision and the conventional laparoscopic group. Interestingly, they found a lower postoperative pain score and shorter median hospital stay in the single-incision group. Although these findings emerge from a randomized controlled trial, they cannot be considered definitive due the low number of patients involved in the study.
Two recent meta-analyses have addressed the issue of comparison between SILS and LCS for both benign and malignant colorectal diseases [71,72]. Both studies have been published in 2012 and thus have included all the comparative studies published to date with the exception of the above mentioned randomized trial by Poon et al. Notwithstanding the heterogeneity of the analyzed studies (14 by Zhou et al. and 15 by Yang et al) in terms of type of procedures performed, indication for surgery, different patient inclusion and exclusion criteria, neither meta-analysis found any significant difference in the incidence of postoperative complications or operative time between single-incision and conventional laparoscopic colectomy. Importantly, they show that patients undergoing single-incision colectomy had a significantly shorter length of hospital stay, significantly shorter incision length, significantly less estimated blood loss, and significantly more lymph nodes harvested during oncological resections. Unfortunately, the two pooled analyses were not able to compare the pain score due to lack of data, the differences in scoring methods and in postoperative care and pain management in the available reported data. However, at least three studies [48,73,74] show a significant decrease in pain scores for patients undergoing single-incision colectomy compared to conventional laparoscopy. The decreased pain score is likely due to less surgical trauma as a consequence of eliminating the additional ports at separate sites on the abdominal wall. There is no meta-analysis regarding cosmetic results due to absence of adequate information on this interesting outcome in the individual studies. Only one study reported cosmetic score results with an advantage for SILS over LCS [23]. However, it is logical to assume that a shorter final incision length in single-incision surgery results in improved cosmetic satisfaction for the majority of the patients.
Another important issue emerging from the literature data is that experienced laparoscopic surgeons have performed almost all single-incision colectomies. This implies that SILS is offered not only to a select group of patients but is also performed by a select group of surgeons. It might appear premature to propose a complex and technically challenging evolution of conventional laparoscopy colectomy when this has yet to be fully accepted as a gold standard in the treatment of colorectal cancer [75]. It must be considered that in 2010, only about 20% of colorectal resections in England and in other countries were performed laparoscopically [76]. Therefore, although the principles of SILS are highly attractive, they might not, at this moment, be transferable and proposed to the general community of surgeons.
The last but not least important concern about single-incision colectomy regards the costs. It is logical to expect an initial increase in costs associated with SILC over conventional laparoscopic surgery since the additional equipment such as single-incision access ports or flexible/articulating instruments are still relatively new. In their analysis of single-incision right-hemicolectomy, Waters et al. [46] found a marginal increase in direct operative cost of US $310 to $410 per case. If patients have a shorter length of hospital stay, and consequently, a quicker return to work and normal activity after single-incision surgery, it is likely there will be an improvement in the cost-effectiveness of SILS in the future.
Most of the current studies on single-incision colectomy for cancer are observational and lack statistical power due to the relatively low number of patients studied. Although meta-analyses can increase the statistical power by pooling results of all available trials, only randomized, controlled studies can provide high levels of evidence. To date, only two randomized controlled studies have compared short-term results between single-incision and conventional laparoscopic surgery and, unfortunately, even these studies have enrolled a very low number of patients. Bearing in mind these limitations, we can still glean several important factors from these published series:
Colonic SILS is technically demanding but the introduction of new specialized equipment including multilumen ports, angled scopes, articulated instruments and instruments of variable length, will eventually reduce this difficulty.
Principles of colonic SILS are attractive and applicable in carefully selected groups of patients, namely with right-sided pathology, low BMI and non-bulky tumors.
In the hands of experienced laparoscopic surgeons, colonic SILS in the above mentioned patients has been demonstrated to be safe and feasible with rates of surgery-related complications and mortality, operative time and oncological adequacy comparable with those of conventional laparoscopy.
Two meta-analyses and one randomized controlled study provide evidence in support of some advantages of SILS over conventional laparoscopy, namely, shorter length of hospital stay, significantly shorter incision length and significantly less estimated blood loss; other hypothesized benefits, such as reduction in postoperative pain and improvement of cosmesis remain unproven.
Further high-powered randomized studies comparing SILS and LCS by using standardized outcome assessment tools are needed to confirm or not the above-mentioned results. But one thing is certain: we will not see the same dramatic clinical advantages with the passage from LCS to SILS as we saw with the advent of laparoscopic technique over open surgery.
Furthermore, the more complex the procedure performed by single-incision surgery, the more likely are there to be advantages in comparison with conventional laparoscopic procedures. In this prospective, a possible field of investigation might be the assessment of systemic stress response of single-incision versus conventional laparoscopy in colorectal surgery. The reduced parietal trauma and manipulation of the peritoneum could decrease the postoperative inflammatory response to surgical stress and as a consequence, more efficient immunocompetency against tumor cells might be maintained since the earliest postoperative days [77,78]. All these factors might influence the long-term oncological results of SILS with a potential improvement in survival rates of patients operated on for colorectal cancer.
The amount of energy consumed in the world has been steadily increasing in the recent decades, and the nonrenewable fossil energy sources account for over 80% of it [1]. In view of this, the search for efficient, environmentally appropriate methods for the generation of renewable energy is a vital present-day scientific problem [2]. One such promising trends is fuel cells [3, 4], the operation of which is directly bound up with the availability of high-purity hydrogen.
\nAt the present time, the wide use of pure hydrogen is economically inexpedient in comparison, e.g., with the use of natural gas, because of the high cost of its production. The industrial method for hydrogen production by the electrolysis of alkaline aqueous solutions [5] has a number of disadvantages, such as the large expenditure of energy, low efficiency of the process, and the necessity of using noble metals as catalysts. Low carbon steel, which is corrosion-nonresistant in alkaline medium, and nickel also possess a catalytic effect in the hydrogen evolution reaction [6]; nevertheless, the problem of search for electrode materials with lower hydrogen evolution overpotential and high corrosion resistance remains vital. For instance, platinum group catalysts can be replaced by cheaper materials, such as nickel, molybdenum, and iron-chromium and iron-manganese alloys, in electrolysis in ionic liquids [7]. However, if the high cost of ionic liquids themselves is taken into account, there is no considerable reduction in the cost of materials for pure hydrogen production.
\nIn the general form, the hydrogen electroreduction process in an alkaline medium is described by the Volmer (1)—Heyrovsky (2)—Tafel (3) mechanism with the following stages:
\nThe rate of electrocatalytic reaction depends on the energy of adsorbed species, i.e., on the energy of hydrogen atoms. The plot of the exchange current density of hydrogen evolution reaction against hydrogen-metal bond energy passes through a maximum and has a volcano-like shape (Figure 1).
\nDependence of the exchange current density of hydrogen evolution reaction in acid solutions against hydrogen-metal bond energy. Reprinted with permission from Ref. [8].
At low Ме▬Н bond energy, the process is controlled by the discharge step, reaction (1). At very high Ме▬Н bond energy, the process is controlled by the electrochemical desorption step, reaction (2). On nickel, cobalt, and iron, the rate-determining step changes from reaction (1) to (2) with increasing polarization. Thus, the most important parameter that determines electrocatalytic activity is the energy of bonding of adsorbed species to the catalyst [9]. When catalysts consisting of two metals are used, the formation of several alloy types, such as mechanical mixtures, solid solutions, and intermetallics is possible. From an analysis of the mechanism of electrocatalytic processes, metal-metal bond energy, and the properties of different alloy types, the authors of [9] conclude that the alloys formed by the metals that are on the different branches of the volcano plot and especially the alloys formed by d-metals with unoccupied d-orbitals (of groups IV–VI) and d-metals of group VIII with a large number of filled d-orbitals possess electrocatalytic activity.
\nIt is known from literature that transition-metal alloys, viz. alloys of iron subgroup metals with molybdenum and tungsten, which show electrocatalytic properties with respect to hydrogen reduction reaction both in acidic [10, 11, 12, 13] and in alkaline aqueous solutions [14, 15, 16, 17], meet these requirements, and that the use of the electrochemical method for the deposition of thin alloy coatings makes it possible to reduce the cost of electrode materials and hence the cost of produced hydrogen.
\nThe synergetic action of alloys in comparison with individual metals is explained by researchers not only by the type of formed alloy and its chemical composition but also by the difference in the mechanism of hydrogen electroreduction on the metals, as well as by the phenomenon of interfacial diffusion of adsorbed hydrogen, hydrogen spillover. The authors of [18] showed the frequent occurrence of this phenomenon in various catalytic processes and catalyst types. Spillover is called the transport of active species, sorbed or formed on one phase, to another phase, which does not sorb and form these species. A study of the synergetic effect of alloys of cobalt and nickel with molybdenum and tungsten with allowance for hydrogen spillover was carried out in [19] for hydrodesulphurization reaction as an example, and it was suggested that different process stages occur on different catalyst phases, between which hydrogen spillover takes place. The spillover phenomenon is of great practical importance, the study of which will help to design new multiphase catalysts, where the catalytic reaction takes place by interfacial diffusion.
\nAs applied to the alloys of molybdenum and tungsten with iron group metals, the spillover phenomenon can account for the synergetic effect of these alloys, in the case of which the discharge step on Mo(W) takes place quickly, and on Co(Ni, Fe), the electrochemical desorption step is fast. Thus, in order that this mechanism may be effected, the active centers of different nature must be at the distance from one another that makes possible the surface diffusion of hydrogen adatoms, and hence the alloy must be a solid solution or an intermetallic.
\nNickel is the most commonly used cathode material in electrolyzers for hydrogen production [20] due to its catalytic properties, corrosion resistance in alkaline medium, and low cost. A possible way of intensifying the process and improving the required properties is electrode surface modification by molybdenum and tungsten alloys; therefore, many papers are devoted to the study of the electrodeposition and catalytic activity of NiMo and NiW alloys. For instance, the authors of [21] studied the electrodeposition of a NiMo alloy on a copper and a nickel substrate from a citrate electrolyte with рН 9.5 and a concentration ratio of the metals of 1/12. The best catalytic activity was found for a coating containing 41 wt.% molybdenum, and it was shown that the hydrogen evolution overpotential at the obtained alloy is lower compared with pure nickel in the model 1 М NaOH solution. In the study [22], a citrate electrolyte with рН 6.0 was also used, and it was shown that it is possible to deposit an alloy containing 28.5 аt.% Мо, which reduces the hydrogen evolution overpotential in 8 M NaOH at 90°С from 122 to 21 mV·dec-1 relative to nickel. The authors of [23] found that when a SAS is added to a citrate-ammonia electrolyte for deposition, nanocrystalline coatings having catalytic activity at a molybdenum content of 19.59 аt.% can be obtained. Chialvo and co-authors [24] studied the catalytic activity of thermal NiMo alloys as a function of the amount of molybdenum (0–25 аt.%) and showed that the higher the Мо content, the lower the hydrogen overpotential. From an analysis of literature data, it can be concluded that there is no unambiguous dependence of electrocatalytic activity on the chemical composition of the coating; for each particular deposition electrolyte, activity is proportional to the molybdenum content, but from the comparison of a large number of papers, it becomes clear that the determining factor is electrolysis conditions, which determine the morphology, the true surface area, the presence of cracks, or an oxide phase on the alloy surface. Therefore, the catalytic properties of electrocatalytic alloys are determined experimentally in each particular case.
\nOn the basis of investigations carried out by the authors of [25], it was concluded that molybdenum-bearing alloys are more active in the hydrogen evolution reaction in alkaline medium than tungsten-bearing alloys. When investigating the properties of Ni-Mo, Ni-W, Co-Mo, and Co-W alloys, it was also found that cobalt alloys show a higher catalytic activity than nickel alloys.
\nThe main characteristics of electrocatalytic activity in HER are reaction exchange current and hydrogen reduction overpotential. Therefore, the main method for studying this process is voltammetry.
\nIn the study [26], an investigation on the electrocatalytic properties of Co-W alloys electrodeposited from a polyligand citrate-pyrophosphate electrolyte had been carried out. The coatings were deposited in a solution containing 0.1 mol L−1 of CoSO4, 0.2 mol L−1 of Na2WO4, 0.2 mol L−1 of Na3Cit (where Cit—citrate ions), 0.2 mol L−1 of K4P2O7, 0.5 mol L−1 of Na2SO4 and in solutions containing SASs: 2 mL L−1 of water-soluble resin neonol, whose efficiency was shown when electrodepositing Co-W alloys from a citrate-ammonia electrolyte [27], and 1.5 g L−1 and 4.5 g L−1 of a nonionic SAS, OP-10 emulsifier. All experiments were performed under forced convection conditions in a current density range of 5.0–30.0 mА сm−2 at 50°С and electrolyte рН 8.5.
\nIt can be seen from Figure 2 that the composition of the coatings deposited from a citrate-pyrophosphate electrolyte is constant regardless of deposition current density and addition of SASs. All coatings containing on an average 22 аt.% W, nevertheless, differ in the current efficiency of their deposition and in the morphology of the produced surface. A small increase in current efficiency for alloys is observed in the case of adding a SAS (neonol or OP-10) to the electrolyte. For instance, at 5.0 mА сm−2 in the presence of neonol, the current efficiency reaches 68%, and a compact, bright, adherent coating is formed. The addition of OP-10 has a noticeable effect only at a concentration of 4.5 g L−1.
\nDependence of the composition (a) and current efficiency (b) of Co-W alloys obtained from electrolyte: 1—without additives; 2—neonol; and 3 and 4—OP-10 (1.5 and 4.5 g L−1) on the deposition current density.
The addition of SASs to the electrolyte and deposition current density affects greatly the quality and morphology (Figure 3). For instance, in the electrolyte without additives at a current density of 5.0 mА сm−2, compact bright coatings are deposited. When the current density is increased to 10.0 mА сm−2, the coating becomes more stressed, and microcracks appear, and at 30.0 mА сm−2, the formation of spherulites is observed. The addition of neonol makes it possible to obtain high-quality fine-crystalline deposits in a wider current density range, and the addition OP-10, on the contrary, facilitates the formation of spherulites and favors surface development.
\nMicrophotographs of the surface of alloys obtained from electrolytes (a) without additives and (b) neonol at a current density of 10.0 mА сm−2 and (c) OP-10 at 30.0 mА сm−2.
The electrocatalytic properties of СоW coatings in the hydrogen reduction reaction were investigated by stationary voltammetry in 1.0 and 6.0 mol L−1 KОН solutions because KOH is used in industrial water electrolysis, and under experimental conditions, i.e., at room temperature, the solution has a maximum electrical conductivity at 28 wt.% KОН.
\nFigure 4a shows a considerable decrease in hydrogen overpotential on CoW alloys relative to electrolytic cobalt. For instance, at the current density of 30.0 mА сm−2, the overpotential decreases by 360 mV. As one would expect, a higher electrocatalytic activity is observed for the coating with more developed surface with spherulites morphology.
\n(a) Volt-ampere curves for the electroreduction of hydrogen in a solution of 1.0 mol L−1 KOH on cobalt (1) and CoW alloys (2 and 3) electrodeposited from the electrolyte without additives at 10.0 and 20.0 mA cm−2, respectively. (b) Volt-ampere curves for the electroreduction of hydrogen in 6.0 mol L−1 KOH solution on CoW alloys, obtained from electrolytes: 1—without additives; 2—neonol; and 3 and 4—OP-10 (1.5 and 4.5 g L−1) at a current density of 10.0 mA cm−2.
Figure 4b shows the effect of SASs added to an electrolyte for the deposition of CoW alloys on their electrocatalytic properties in a solution analogous to industrial electrolyte for hydrogen production. It can be seen that in this particular case, the addition of SAS rather has adverse effects, i.e., smoothing the surface during electrodeposition improves the mechanical and corrosive properties of the coating, but reduces its true surface area.
\nIn the study [28], cobalt and Со-Мо alloys were deposited from a citrate-pyrophosphate electrolyte, proposed earlier [29], with the different concentration ratio of the metals in the solution: [Co]:[Mo] = 20:1; 10:1: 5:1; 1:1 in a current density range of 10–100 mА сm−2 at 50°С. The studies of hydrogen electroreduction on Со-Мо alloys were carried out in solutions with different mineralization and рН, viz. 0.01 mol L−1 H2SO4; 0.5 mol L−1 Na2SO4; and 1.0 mol L−1 KOH. The voltammetric measurements for the determination of the kinetic parameters of hydrogen reduction were made at 25°С. The current-potential curves were recorded under potentiostatic conditions with a step of 20 mV. Before each experiment, argon was passed through the solution for 30 min.
\nIn order to show clearly the catalytic effect of the alloy in comparison with an individual metal, current-potential curves of hydrogen reduction on pure cobalt deposited from a citrate-pyrophosphate electrolyte at a current density of 30 mА сm−2 and a temperature of 50°С have been obtained.
\nFigure 5 shows current-potential curves of hydrogen electroreduction in an acidic, an alkaline, and a neutral medium on electrolytic cobalt cathodes and cathodes made of Со-Мо alloys electrodeposited at the same current density and temperature.
\nStationary current-potential curves of the electroreduction of hydrogen evolution on electrolytic cobalt (a) and Co-Mo alloys (b) with the ratio [Mo]/[Mo] + [Co] = 0.33 electrodeposited at the current density 30 mA cm−2, in media with different pH: 1—H2SO4, 2—KOH, and 3—Na2SO4.
Because of differences in electroreduction mechanism at different pH values, the lowest hydrogen evolution overpotential on cobalt is observed in an acidic medium and the highest in a neutral medium, as is the case with the dependence obtained for a mercury electrode and described in [30]. In the case of cobalt cathode, the coefficient b of the Tafel portion of the polarization curve for the acidic, alkaline, and neutral media was 0.122, 0.142, and 0.125 V, and the exchange current density was 1.93, 4.59 × 10−2 and 6.31 × 10−3 mА сm−2, respectively.
\nFigure 5 shows a considerable decrease in hydrogen evolution overpotential on the alloy. For instance, at the current density of 10 mА сm−2, the overpotential value in the alkaline medium is lower by over 200 mV.
\nThe plots shown in Figure 6 have been obtained on alloys electrodeposited at different current densities of 10–100 mА сm−2. The abscissa of the figure gives the ratio of the amounts of the metals in the alloy, and not the exact percentage because of the peculiarities of EDX analysis, in which the coating surface layer, on which a large amount of oxygen and carbon are adsorbed. The adsorbed light elements can be removed by polishing the surface or treating it with argon ions. Both in this and in the initial case, the ratio of the metals in the alloy remains constant, as was shown in [17], with a coating depth of up to 100 nm. Thus, the ratio of molybdenum and cobalt in the surface layer, determined by EDX analysis, corresponds to the volumetric chemical composition of the alloy.
\nDependence of the exchange current densities of the hydrogen electroreduction reaction on the ratio of molybdenum to cobalt in alloys electrodeposited at current densities of 10, 30, and 100 mA cm−2 from the solution with a [Co]:[Mo] ratio of 1:1 in various media: 1—H2SO4, 2—KOH, and 3—Na2SO4.
In the alloys deposited from an electrolyte with the concentration ratio [Co]:[Mo] = 1:1, the amount of molybdenum decreases and the exchange current density of the hydrogen reduction reaction increases with increasing deposition current density, which can be accounted for in terms of the value which the surface morphology and the true electrode area have, as was shown in [17]. Figure 7 shows surface micrographs of alloys electrodeposited at two current densities of 10 and 100 mА сm−2. It can be seen that at a low current density, smooth, fine-crystalline, and bright coatings are deposited in spite of the presence of microcracks. Increasing the deposition current density to 100 mА сm−2 results in the formation of spherulites and considerable surface development. This regularity is observed for all investigated solutions.
\nThe morphology of Co-Mo alloys precipitated from electrolytes [Co]:[Mo] = 1:1 (a and b) and [Co]:[Mo] = 5:1 (c and d) at current densities of: a and c—10 mA cm−2; b and d—100 mA cm−2 and the ratio of metals [Mo]/[Mo] + [Co] equal to 0.39, 0.27, 0.28, and 0.21, respectively.
The conclusion that the electrocatalytic activity decreases with increasing refractory metal content may contradict papers, published earlier, on the properties of Co-Mo coatings [17, 14]. However, attention should be called on how the coating composition was changed. There are several ways of influencing the chemical composition of alloys, viz. changing the electrolyte composition and pH, temperature, current density, hydrodynamic regime, etc. For instance, in the study [14], a change in alloy composition is achieved by changing both deposition current density and electrolyte composition and in the study [17], by changing pH and, hence, the concentration ratio of different complex species that are able to be discharged to form an alloy. Thus, it is impossible to obtain a rigorous dependence of catalytic activity on the composition of coating deposited under different conditions, because the electrolysis conditions influence not only chemical but also phase composition, which in turn influences the properties of the alloy as a whole.
\nThe effect of change in the composition of the solution for alloy electrodeposition on the electrocatalytic properties is clearly seen in Figure 8, which shows current-potential curves of hydrogen electroreduction on cobalt and alloys deposited at a current density of 30 mА сm−2 from electrolytes containing different sodium molybdate concentrations. It is seen from the figure that the highest hydrogen evolution overpotential is observed on cobalt deposits and the lowest on the alloy deposited from the electrolyte with [Co]:[Mo] = 10:1. The kinetic parameters of hydrogen electroreduction in an alkaline medium are presented in Table 1.
\nPolarization curves obtained in KOH solution on cobalt (1) and Co-Mo alloys with the ratio of metals [Mo]/[Mo]+[Co] equal to (2)—0.11, (3)—0.19, (4)—0.23, and (5)—0.33, respectively, electrodeposited at 30 mA∙cm−2 from electrolytes [Co]:[Mo] = 20:1, 10:1, 5:1, 1:1, respectively.
Electrolyte | \njdep. (mА сm−2) | \nЕ0 (V) | \nа | \nb | \nj0 (mА сm−2) | \n[Мо]/([Мо] + [Со])* | \n
---|---|---|---|---|---|---|
Co | \n30 | \n−0.821 | \n0.190 | \n0.142 | \n4.59 × 10−2 | \n— | \n
[Co]:[Mo] = 20:1 | \n10 | \n−0.910 | \n0.181 | \n0.134 | \n4.46 × 10−2 | \n0.22 | \n
30 | \n−0.985 | \n0.038 | \n0.077 | \n3.21 × 10−1 | \n0.11 | \n|
[Co]:[Mo] = 10:1 | \n10 | \n−0.940 | \n0.125 | \n0.091 | \n9.23 × 10−2 | \n0.25 | \n
20 | \n−1.005 | \n0.045 | \n0.058 | \n1.67 × 10−1 | \n0.23 | \n|
30 | \n−1.025 | \n0.025 | \n0.056 | \n3.58 × 10−1 | \n0.19 | \n|
[Co]:[Mo] = 5:1 | \n10 | \n−0.920 | \n0.130 | \n0.155 | \n1.25 × 10−1 | \n0.28 | \n
30 | \n−0.980 | \n0.050 | \n0.062 | \n1.56 × 10−1 | \n0.23 | \n|
100 | \n−1.000 | \n0.035 | \n0.053 | \n2.19 × 10−1 | \n0.21 | \n|
[Co]:[Mo] = 1:1 | \n10 | \n−0.900 | \n0.189 | \n0.146 | \n5.08 × 10−2 | \n0.39 | \n
20 | \n−0.935 | \n0.110 | \n0.089 | \n5.81 × 10−2 | \n0.37 | \n|
30 | \n−0.980 | \n0.083 | \n0.080 | \n9.17 × 10−2 | \n0.33 | \n|
40 | \n−0.965 | \n0.069 | \n0.077 | \n1.27 × 10−1 | \n0.30 | \n|
100 | \n−1.010 | \n0.043 | \n0.068 | \n2.33 × 10−1 | \n0.27 | \n
Kinetic parameters of hydrogen reduction reaction in a 1 mol L−1 KОН.
The ratio of the metals was calculated based on their atomic fraction in alloys.
Here, jdep. is the current density of alloy deposition; Е0 is the stationary potential of the alloy in a КОН solution; а and b are coefficients in the Tafel equation; and j0 is hydrogen exchange current density.
The difference in the value of hydrogen exchange current on alloys with the same chemical composition is seen in Figure 9.
\nThe dependence of the exchange current of the hydrogen reduction in a 1.0 mol L−1 KOH solution (1 and 2) and the current efficiency (3 and 4) of the Co-Mo alloys electrodeposited in the electrolytes [Co]:[Mo] = 5:1 and [Co]:[Mo] = 1:1 on the ratio of metals in the alloy.
In Figure 9, attention should be called on how the current efficiency of the deposition of the alloy and its electrocatalytic activity correlate with each other. In spite of the fact that the current efficiency was measured for a citrate-pyrophosphate electrolyte for deposition, this electrolyte is a weakly alkaline salt solutions, in which the alloys that are formed also exhibit electrocatalytic activity against the parallel cathodes process, with hydrogen electroreduction; therefore, the plots shown in Figure 9 are of antibate character. Therefore, alloys, electrodeposited at high current densities up to 100 mA cm−2 and having the highest catalytic activity (for all deposition electrolytes) are deposited with the lowest current efficiency.
\nFrom the obtained data, it can be concluded that in the case of Со-Мо alloys electrodeposited from citrate-pyrophosphate electrolytes, the hydrogen exchange current decreases for each particular electrolyte with increasing amount of molybdenum in the alloy. However, in a series of electrolytes with the different concentration ratio of the discharging metals, the alloys that differ greatly in chemical composition can have the same electrocatalytic activity; this can be seen in Figure 10, which shows values of hydrogen exchange currents and stationary potentials for alloys deposited at the same current density, but from different electrolytes.
\nThe dependence of the exchange current (1 and 2) and the stationary potential (3 and 4) in the KOH solution on the molybdenum and cobalt ratio in alloys deposited at current densities, mА cm−2. 1: 3—30; and 2: 4—10.
An extreme form is typical both of the plots of hydrogen exchange current density vs. the ratio of the alloy components and of the stationary potential values of the alloy in the КОН solution.
\nThus, the optimal electrolyte for the making of electrocatalytic Со-Мо alloys is the electrolyte with a cobalt and molybdenum concentration ratio of 10:1, which occupies an intermediate position in the series of investigated solutions; so, increasing or decreasing the concentration of sodium molybdate and hence of molybdenum in the alloy results in the deterioration of the catalytic properties of the coating.
\nIt is known [10] that the electrocatalytic activity of electrode material can be increased by several ways, e.g., by increasing the true working surface area of the catalyst, viz. by making the catalyst not in the form of a continuous film, but in the form of nanofibers [31]. The true surface area must be estimated when fabricating continuous alloy coatings, as this was done in [17]; it should be noted, however, that the factor of surface development is not determining in the ascertainment of the causes of the electrocatalytic activity of the materials under investigation. Another important factor is the nature of the metals comprising the alloy, which was shown in [25], but the physicochemical properties of one metal do not account for the synergetic effect in the use of alloys. The phenomenon that describes most reliably the synergetic action of two or more metals is spillover effect, which was described in [10, 11, 12]. Since hydrogen evolution occurs on Со and Мо with different rate-determining steps, as was said above, the occurrence of hydrogen spillover makes it possible to bring about a fact reaction (1) on molybdenum atoms and a rapid electrochemical desorption (2) on cobalt atoms.
\nBecause of this, the synergetic effect of the alloy will manifest itself when the atoms are arranged in an optimal manner to perform sequential reaction steps. This is possible when the alloy is an intermetallic, an amorphous phase, or solid solutions with nanosized crystals.
\nWhen we attempted to investigate the coatings obtained by us by X-ray phase analysis, we have not obtained somewhat well-defined peaks of phases, i.e., the coatings were either very fine-crystalline, below the device sensitivity level, or amorphous. However, different properties (e.g., corrosion or magnetic properties) of Co-Mo alloys of the same composition have also been obtained by us earlier. Their phase composition has been studied by us by stripping analysis and shown in [32].
\nSome of the main characteristics of modern catalytic materials are not only their activity in the desired reaction but also mechanical strength and corrosion resistance in aggressive media; therefore, the comprehensive investigation of the physicochemical properties of the electrode material is an important scientific and technical problem.
\nIn the study [26], the corrosion characteristics of electrolytic Co-W alloys deposited from a citrate-pyrophosphate electrolyte in 3.5% NaCl and 6 mol L−1 KOH solutions at 25°С have been determined by EIS and stationary voltammetry (Figure 11).
\nElectrochemical impedance spectra (a) and current-potential curves (b) obtained in the case of corrosion of coatings electrodeposited from a citrate-pyrophosphate electrolyte at the current densities mА cm−2: 1—5.0; 2—10.0; and 3—20.0.
The impedance hodographs obtained at a stationary potential in a corrosive medium can be described by a circuit comprising the ohmic resistance of the solution, charge transfer (corrosion) resistance, and a constant phase element. The corrosion parameters calculated in accordance with this equivalent circuit are listedTable 2.
\n\n | j (mА сm−2) | \nW (аt.%) | \nR (kОhm сm−2) | \nRp (kОhm сm−2) | \nЕcorr (V) | \nJcorr × 105 (А сm−2) | \n
---|---|---|---|---|---|---|
1 | \n5.0 | \n23.3 | \n18.0 | \n41.2 | \n−0.782 | \n1.35 | \n
2 | \n10.0 | \n24.0 | \n18.8 | \n6.9 | \n−0.834 | \n8.53 | \n
3 | \n20.0 | \n20.8 | \n12.8 | \n16.6 | \n−0.786 | \n5.24 | \n
Corrosion parameters of alloys in a 3.5% NaCl solution.
Here, j is alloy deposition current density; W is tungsten content, аt.%; R is corrosion resistance determined by the impedance method; Rp is corrosion resistance determined by voltammetry; Еcorr is corrosion potential; and jcorr is corrosion current density.
The coating deposited at a current density of 5.0 mА сm−2 has the highest corrosion stability because in the region of kinetic control of electrochemical reaction, most fine-crystalline and compact deposits are formed. Since the chemical composition of the coatings deposited from a citrate-pyrophosphate electrolyte is almost constant, the dependence of polarization resistance on deposition current density can be attributed to a difference in surface morphology and the appearance of microcracks on increasing the deposition current. On the whole, the corrosion rate of the obtained alloys is comparable with that in an analogous solution of electrolytic chromium deposited from Cr(III) and Cr(VI) baths in the study [33] (Figure 12).
\nSpectra of electrochemical impedance (a) and current-potential curves (b), obtained in the case of corrosion in a 6.0 mol L−1 KOH solution, for coatings electrodeposited at a current density of 10.0 mA cm−2 from electrolytes 1—no additives; 2—neonol; 3 and 4—OP-10 (1.5 and 4.5 g L−1).
The parameters of the corrosion process, determined by the electrochemical impedance method, have been calculated on the basis of an equivalent circuit comprising the ohmic resistance of the solution, corrosion resistance, a constant phase element, and Warburg impedance (Table 3).
\nElectrolyte | \nW (аt.%) | \nR (kOhm сm−2) | \nRp (kOhm сm−2) | \nЕcorr (V) | \nJcorr × 103 (А сm−2) | \n
---|---|---|---|---|---|
1 | \n24.0 | \n0.92 | \n0.58 | \n−1.03 | \n0.84 | \n
2 | \n23.7 | \n0.46 | \n0.37 | \n−1.05 | \n0.11 | \n
3 | \n24.0 | \n0.34 | \n0.40 | \n−1.04 | \n0.17 | \n
4 | \n22.6 | \n0.40 | \n0.48 | \n−1.03 | \n0.12 | \n
Corrosion parameters of alloys in a 6 mol L−1 КОН solution.
The corrosion studies, carried out by us, of CoW alloys in a 6.0 mol L−1 КОН solution showed that the corrosion resistance in a concentrated КОН solution (Figure 12) is two order of magnitude lower than in a model NaCl solution; nevertheless, the coatings can be considered corrosion proof. It was noted that the coatings obtained for the experiment are of the worst quality in comparison with others, since they are intermediate at the transition from fine crystalline to spherulite deposits. The deposits of these two types are dense and smooth, and only at 10.0 mА сm−2, the largest number of cracks is observed, which accordingly affects the properties of coatings; nevertheless, the coatings have a low corrosion rate and are passivated in alkaline solution.
\nTo determine the corrosion properties of electrolytic Со-Мо alloys in the study [34], the coatings were deposited from a citrate-pyrophosphate electrolyte with different concentration ratios of the metals: [Co]/[Mo] = 1/1 and [Co]/[Mo] = 5/1. The aim of the authors was a large percentage of a component having ferromagnetic properties, i.e., cobalt. To fabricate cobalt-rich alloys, electrolytes with low sodium molybdate content and, hence, with small amount of molybdenum in the coating are used.
\nAs is seen from Figure 13, the amount of molybdenum in the alloy electrodeposited from an electrolyte at [Co]/[Mo] = 5/1 decreased relative to the alloy deposited from an electrolyte with [Co]/[Mo] = 1/1; in this case, however, no direct proportionality between the molybdenum content of the alloy and solution is observed. For instance, the concentration ratio of molybdate and cobalt in the electrolyte was 0.2 and changed from 0.4 to 0.27 in the coating. The amount of cobalt in the deposit changes only slightly on increasing the current density, but the percentage of nonmetallic impurities, mainly oxygen, increases, which affect the internal stresses in the deposit. Nevertheless, this change in the concentration ratio of the metals in the solution leads to a great increase in current efficiency for the alloy at low current densities (Figure 13b). Thus, it can be stated that in terms of the cobalt content of the alloy, the most optimal conditions for the deposition of magnetic coatings are current densities of 10–50 mА сm−2.
\nDependence of the ratio of the metals content (a) and current efficiency (b) for alloys electrodeposited from electrolytes with a concentration ratios [Co]/[Mo] = 1/1 and [Co]/[Mo] = 5/1 on current density.
The corrosion test of the obtained coatings was carried out in a sulfate-chloride solution. The calculation of corrosion resistance from electrochemical impedance data has been performed on the basis of an equivalent circuit comprising the ohmic resistance of the solution, charge transfer resistance, and a constant phase element.
\nAlloy samples electrodeposited from an electrolyte with [Co]/[Mo] = 5/1 with increasing current density, i.e., with decreasing molybdenum content (Figure 13, curve 2), and an alloy electrodeposited from an analogous citrate electrolyte containing no pyrophosphate at 30 mА сm−2, have been investigated. Figure 14 and Table 4 show no clear correlation between the molybdenum content of the alloy and corrosion resistance. Besides, the coatings deposited from solutions with the same ratio of the metals in the presence and absence of pyrophosphate are similar in anticorrosion properties despite the difference in their chemical composition.
\nStationary current-potential curves (a) and electrochemical impedance spectra (b) of the corrosion of alloys deposited from polyligand electrolyte (1–3) and a citrate electrolyte (4) at the deposition current densities, mА cm−2: 1—10; 2 and 4—30; and 3—50.
Electrolyte | \nj (mА сm−2) | \nМо (аt.%) | \nR (Оhm) | \nRp (Оhm) | \nЕcorr (V) | \nJcorr (А сm−2) | \n
---|---|---|---|---|---|---|
Citrate-pyrophosphate | \n10 | \n21.5 | \n5.05 × 102 | \n2.97 × 103 | \n−0.627 | \n3.58 × 10−4 | \n
30 | \n17.4 | \n5.71 × 103 | \n1.77 × 104 | \n−0.804 | \n829 × 10−6 | \n|
50 | \n16.0 | \n7.02 × 102 | \n3.55 × 102 | \n−0.677 | \n6.40 × 10−4 | \n|
Citrate | \n30 | \n23.9 | \n4.57 × 103 | \n8.06 × 103 | \n−0.804 | \n2.83 × 10−5 | \n
Dependence of the corrosion parameters of Со-Мо alloys on alloy composition.
Here, j is deposition current density.
The anticorrosion resistance of Co-Mo coatings is usually associated with the percentage content of molybdenum in them as a more corrosion-resistant metal, and the magnetic properties of coatings—with a cobalt content as a metal with ferromagnetic properties. However, the functional properties of coatings can depend not only on the chemical composition of the alloy but also on its phase composition, morphology, thickness, porosity, and other factors.
\nWhen studying the corrosion and magnetic properties of Со-Мо coatings [32] deposited from a citrate-pyrophosphate electrolyte, it was found that for the coatings obtained under different electrolysis conditions and having the same chemical composition, the corrosion stability and magnetic parameters are different; it was suggested that the properties of the alloy largely depend on its phase composition.
\nIn the study, the corrosion and magnetic properties of coatings with same Mo content of the alloy (21.2 аt.%), deposited from a citrate-pyrophosphate electrolyte under different electrolysis conditions, have been investigated. The corrosion stability of the coatings was studied in a solution containing 7 g L−1 Na2SO4 and 7 g L−1 NaCl at рН 6.0 and 24 ± 1°С (Table 5). The magnetic properties (Table 6) of the obtained deposits were determined by means of a vibrating sample magnetometer in fields of up to 20 kOe at room temperature (Table 5).
\nDeposition electrolyte | \nj (mА сm−2) | \nt (°С) | \nRр (Оhm) | \nЕcorr (V) | \nJcorr (А сm−2) | \n
---|---|---|---|---|---|
[Co]/[Mo] = 1/1 | \n30 | \n25 | \n2.71 × 103 | \n−0.804 | \n8.44 × 10−5 | \n
[Co]/[Mo] = 1/1 | \n40 | \n50 | \n9.82 × 102 | \n−0.808 | \n2.54 × 10−4 | \n
[Co]/[Mo] = 5/1 | \n10 | \n50 | \n2.97 × 103 | \n−0.627 | \n3.58 × 10−4 | \n
Corrosion properties of alloys having the same chemical composition (21.2 аt.% Мо).
The magnetic characteristics of such Alloys are also given. Their calculated values are listed in Table 6. The main criteria for evaluating the properties of soft-magnetic materials are low coercive force, low remanent magnetization and high saturation magnetization, as well as the ability to reach saturation magnetization in low intensity fields. It is evident from Table 6 that the largest saturation magnetization values—927 Gs were obtained at a magnetic field intensity of 3 kOe for the alloys deposited from an electrolyte with a ratio of 5:1. For the coatings deposited from an electrolyte with a ratio of 1:1, no saturation magnetization is observed even at 20 kOe; the maximum value obtained under experimental conditions for alloys deposited at 25° and 50°С was 113 and 290 Gs, respectively. Thus, it can be concluded that the alloy deposited from an electrolyte with the concentration ratio of the metals [Co]/[Mo] = 5/1. We assumed that such a difference in functional properties for the coatings having the same chemical composition may be due to a difference in their phase composition.
\nDeposition electrolyte | \nj (mА сm−2) | \nt (°С) | \nН (Oe) | \nMR (Gs) | \nМS (Gs) | \n
---|---|---|---|---|---|
[Co]/[Mo] = 1/1 | \n30 | \n25 | \n155 | \n5.0 | \n113 | \n
[Co]/[Mo] = 1/1 | \n40 | \n50 | \n117 | \n20.0 | \n290 | \n
[Co]/[Mo] = 5/1 | \n10 | \n50 | \n102 | \n252 | \n927 | \n
Magnetic properties of alloys having the same chemical composition (21.2 аt.% Мо).
Here, Н is coercive force, MR is remanent magnetization, and МS is saturation magnetization.
To study the phase composition, the electrochemical method of linear stripping voltammetric analysis (LSVA) was used [35]. An advantage of this method, besides simplicity, is the possibility to follow the dissolution dynamics of the alloy. Before the stripping analysis, a 0.5 μM thick layer of Co or Co-Mo alloys were deposited onto the working electrode from a citrate-pyrophosphate electrolyte with the concentration ratios of the metals [Co]/[Mo] = 1/1 and [Co]/[Mo] = 5/1 at a current density of 10–100 mА сm−2 and a temperature of 25 and 50°С.
\nThe electrolyte for the anodic dissolution of the obtained alloy deposits must meet the following requirements: it must have a high electrical conductivity, be nonaggressive toward the coating, and not cause spontaneous chemical dissolution. In this electrolyte, an electrochemical side reaction paralleling the anodic dissolution of the deposit under investigation must be ruled out. The use of various acids as working solutions was considered inexpedient since the electrochemical process in such electrolytes is paralleled by the chemical dissolution of the coating under analysis. Alkaline solutions are unsuitable for use as working electrolytes because of passivation processes on the surface of samples under investigation. The optimal solution for the anodic dissolution of coatings under investigation is NaCl solution, which makes it possible to obtain on the current-potential curves clear peaks corresponding to the dissolution potentials of the various phases of the alloy. The stripping analysis of coatings was performed in a 0.5 М NaCl solution at 25°С on a rotating disk electrode at a rotational speed of 774 rpm.
\nFigure 15 shows a current-potential curve of the dissolution of freshly deposited cobalt (curve 1) in a 0.5 М NaCl solution. The observed dissolution peaks are traditionally attributed to the complex phase structure of metals and alloys, but their number depends on the electrolyte in which dissolution is performed [35]. The plot of cobalt dissolution current vs. potential exhibits three peaks, which we further use in order to distinguish the peaks of dissolution of the alloy from the peaks of cobalt dissolution. The figure shows plots except the oxygen and chlorine evolution curve. It can be seen that in the case of dissolution of alloys, the magnitude of the peaks and their number are different. For instance, for the alloys deposited from an electrolyte with the same concentration ratio of the metals, the magnitude of peak 1 is the same, but besides it, only one large peak is observed for the alloy obtained at 50°С and 40 mА сm−2, whereas two peaks are observed for the alloy obtained at 25°С and 30 mА сm−2. However, for the alloy deposited from an electrolyte with lower molybdate content, the magnitude of peak 1 is much larger than for other alloys. Based on the potentials of the peaks, the known cathodic quantity of electricity, the phase diagram of the double layer, and stoichiometry, it can be suggested that peaks 1 and 3 relate to cobalt dissolution and peak 2 to the dissolution of a solid solution of the chemical compound СоМо in cobalt.
\nAnodic dissolution curves for pure cobalt (curve 1) and Co-Mo alloys (21.1 at.% Mo) deposited under the following conditions: 2—Co:Mo = 5:1, 50°C, 10 mA cm−2; 3—Co:Mo = 1:1, 25°C, 30 mA cm−2; 4—Co:Mo = 1:1, 50°С, 40 mА сm−2.
Thus, the alloy deposited from an electrolyte containing a small amount of molybdate contains a larger amount of cobalt bound into neither a chemical compound nor a solid solution; this can explain the 200 mV shift of the corrosion potential of this alloy to positive values, i.e., cobalt is a more electropositive metal than molybdenum, as well as the improvement of the magnetic properties of the alloy. The increase in peak 2 indicates an increase in the percentage of the molybdenum-rich phase, which results in the improvement of the corrosion properties of alloys.
\nStripping analysis of alloys deposited from an electrolyte with [Co]/[Mo]=1/1 at different current densities is shown in Figure 16. It is seen from the figure that for the coatings obtained at lower deposition current densities 10–20 mА сm−2, three dissolution peaks are observed. For the alloys deposited at 30 and 40 mА сm−2, only two dissolution peaks are observed. The magnitude of peak 1 remains unchanged, and it can be assumed to correspond to the amount of cobalt that is directly on the electrode surface, i.e., dissolution of the less corrosion-resistant component than the alloy takes place, and since the electrode geometry does not change, the quantity of electricity for dissolution remains constant too. In the remaining alloy phase at different current densities, different redistribution of cobalt between the solid solution and the free α-phase takes place.
\n(a) Anodic current-potential curves of the dissolution of Co-Mo alloys deposited from an electrolyte at [Co]/[Mo] = 1/1 at 50°C at different current densities, mA cm−2: 1—10, 2—20, 3—30, 4—40 and (b) The magnitude of anodic dissolution peaks.
To study the alloy formation process, anodic polarization curves have been obtained for Со-Мо alloys deposited from an electrolyte with [Co]/[Mo] = 1/1 under the conditions corresponding to the maximum current efficiency: a current density of 30 mА сm−2 and at temperature of 50°С [36]. The coatings were deposited during 30, 60, 120, and 210 s (Figure 17). All current-potential curves of the dissolution of Со-Мо alloys exhibit two peaks. As one would expect, the quantity of electricity for the dissolution of the solid solution increases linearly with deposition time. We failed, however, to determine the order of deposition of the components; using this method, it is impossible to either confirm or refute the hypothesis that cobalt deposits first, which catalyzes later the reduction of molybdenum. Under our experimental conditions, an alloy phase which grows uniformly with increasing deposition time is present in the alloy even within a deposition time of 30 s.
\n(a) Anodic current-potential curves of the dissolution of Co-Mo alloys deposited from an electrolyte with [Co]/[Mo]=1/1 at 30 mA∙cm−2 and 50°C at different deposition time, s: 1—30, 2—60, 3—120, 4—210. (b) The magnitude of the anodic dissolution peaks: 1—the first peak, and 2—the second peak.
Electrolytic alloys of molybdenum and tungsten with iron subgroup metals possess catalytic properties in the hydrogen evolution reaction and can be used as a coating which improves the properties of exiting nickel cathodes.
\nFor each particular electrolyte and particular deposition conditions, the activity of the alloy and its corrosion stability increase with the amount of molybdenum, but the comparison of data obtained by different authors does not give a clear correlation.
\nThe properties of alloys depend not only on their chemical composition but also on their phase composition. The alloy containing the same amount of molybdenum, but fabricated under different conditions, has different corrosion and magnetic properties.
\nThe amorphous and nanocrystalline structure of electrolytic alloys makes hydrogen spillover possible, which greatly accelerates the hydrogen reduction process in alkaline electrolytes.
\nElectrolytic coatings of refractory metals alloys have a wide range of physicochemical properties. Controlling the electrolysis modes allows precipitating and accurately controlling the chemical and phase composition of the coatings, and hence producing corrosion-resistant materials for soft magnetic materials, electrocatalysts, and wear-resistant coatings.
\n"Open access contributes to scientific excellence and integrity. It opens up research results to wider analysis. It allows research results to be reused for new discoveries. And it enables the multi-disciplinary research that is needed to solve global 21st century problems. Open access connects science with society. It allows the public to engage with research. To go behind the headlines. And look at the scientific evidence. And it enables policy makers to draw on innovative solutions to societal challenges".
\n\nCarlos Moedas, the European Commissioner for Research Science and Innovation at the STM Annual Frankfurt Conference, October 2016.
",metaTitle:"About Open Access",metaDescription:"Open access contributes to scientific excellence and integrity. It opens up research results to wider analysis. It allows research results to be reused for new discoveries. And it enables the multi-disciplinary research that is needed to solve global 21st century problems. Open access connects science with society. It allows the public to engage with research. To go behind the headlines. And look at the scientific evidence. And it enables policy makers to draw on innovative solutions to societal challenges.\n\nCarlos Moedas, the European Commissioner for Research Science and Innovation at the STM Annual Frankfurt Conference, October 2016.",metaKeywords:null,canonicalURL:"about-open-access",contentRaw:'[{"type":"htmlEditorComponent","content":"The Open Access publishing movement started in the early 2000s when academic leaders from around the world participated in the formation of the Budapest Initiative. They developed recommendations for an Open Access publishing process, “which has worked for the past decade to provide the public with unrestricted, free access to scholarly research—much of which is publicly funded. Making the research publicly available to everyone—free of charge and without most copyright and licensing restrictions—will accelerate scientific research efforts and allow authors to reach a larger number of readers” (reference: http://www.budapestopenaccessinitiative.org)
\\n\\nIntechOpen’s co-founders, both scientists themselves, created the company while undertaking research in robotics at Vienna University. Their goal was to spread research freely “for scientists, by scientists’ to the rest of the world via the Open Access publishing model. The company soon became a signatory of the Budapest Initiative, which currently has more than 1000 supporting organizations worldwide, ranging from universities to funders.
\\n\\nAt IntechOpen today, we are still as committed to working with organizations and people who care about scientific discovery, to putting the academic needs of the scientific community first, and to providing an Open Access environment where scientists can maximize their contribution to scientific advancement. By opening up access to the world’s scientific research articles and book chapters, we aim to facilitate greater opportunity for collaboration, scientific discovery and progress. We subscribe wholeheartedly to the Open Access definition:
\\n\\n“By “open access” to [peer-reviewed research literature], we mean its free availability on the public internet, permitting any users to read, download, copy, distribute, print, search, or link to the full texts of these articles, crawl them for indexing, pass them as data to software, or use them for any other lawful purpose, without financial, legal, or technical barriers other than those inseparable from gaining access to the internet itself. The only constraint on reproduction and distribution, and the only role for copyright in this domain, should be to give authors control over the integrity of their work and the right to be properly acknowledged and cited” (reference: http://www.budapestopenaccessinitiative.org)
\\n\\nOAI-PMH
\\n\\nAs a firm believer in the wider dissemination of knowledge, IntechOpen supports the Open Access Initiative Protocol for Metadata Harvesting (OAI-PMH Version 2.0). Read more
\\n\\nLicense
\\n\\nBook chapters published in edited volumes are distributed under the Creative Commons Attribution 3.0 Unported License (CC BY 3.0). IntechOpen upholds a very flexible Copyright Policy. There is no copyright transfer to the publisher and Authors retain exclusive copyright to their work. All Monographs/Compacts are distributed under the Creative Commons Attribution-NonCommercial 4.0 International (CC BY-NC 4.0). Read more
\\n\\nPeer Review Policies
\\n\\nAll scientific works are Peer Reviewed prior to publishing. Read more
\\n\\nOA Publishing Fees
\\n\\nThe Open Access publishing model employed by IntechOpen eliminates subscription charges and pay-per-view fees, enabling readers to access research at no cost. In order to sustain operations and keep our publications freely accessible we levy an Open Access Publishing Fee for manuscripts, which helps us cover the costs of editorial work and the production of books. Read more
\\n\\nDigital Archiving Policy
\\n\\nIntechOpen is committed to ensuring the long-term preservation and the availability of all scholarly research we publish. We employ a variety of means to enable us to deliver on our commitments to the scientific community. Apart from preservation by the Croatian National Library (for publications prior to April 18, 2018) and the British Library (for publications after April 18, 2018), our entire catalogue is preserved in the CLOCKSS archive.
\\n"}]'},components:[{type:"htmlEditorComponent",content:'The Open Access publishing movement started in the early 2000s when academic leaders from around the world participated in the formation of the Budapest Initiative. They developed recommendations for an Open Access publishing process, “which has worked for the past decade to provide the public with unrestricted, free access to scholarly research—much of which is publicly funded. Making the research publicly available to everyone—free of charge and without most copyright and licensing restrictions—will accelerate scientific research efforts and allow authors to reach a larger number of readers” (reference: http://www.budapestopenaccessinitiative.org)
\n\nIntechOpen’s co-founders, both scientists themselves, created the company while undertaking research in robotics at Vienna University. Their goal was to spread research freely “for scientists, by scientists’ to the rest of the world via the Open Access publishing model. The company soon became a signatory of the Budapest Initiative, which currently has more than 1000 supporting organizations worldwide, ranging from universities to funders.
\n\nAt IntechOpen today, we are still as committed to working with organizations and people who care about scientific discovery, to putting the academic needs of the scientific community first, and to providing an Open Access environment where scientists can maximize their contribution to scientific advancement. By opening up access to the world’s scientific research articles and book chapters, we aim to facilitate greater opportunity for collaboration, scientific discovery and progress. We subscribe wholeheartedly to the Open Access definition:
\n\n“By “open access” to [peer-reviewed research literature], we mean its free availability on the public internet, permitting any users to read, download, copy, distribute, print, search, or link to the full texts of these articles, crawl them for indexing, pass them as data to software, or use them for any other lawful purpose, without financial, legal, or technical barriers other than those inseparable from gaining access to the internet itself. The only constraint on reproduction and distribution, and the only role for copyright in this domain, should be to give authors control over the integrity of their work and the right to be properly acknowledged and cited” (reference: http://www.budapestopenaccessinitiative.org)
\n\nOAI-PMH
\n\nAs a firm believer in the wider dissemination of knowledge, IntechOpen supports the Open Access Initiative Protocol for Metadata Harvesting (OAI-PMH Version 2.0). Read more
\n\nLicense
\n\nBook chapters published in edited volumes are distributed under the Creative Commons Attribution 3.0 Unported License (CC BY 3.0). IntechOpen upholds a very flexible Copyright Policy. There is no copyright transfer to the publisher and Authors retain exclusive copyright to their work. All Monographs/Compacts are distributed under the Creative Commons Attribution-NonCommercial 4.0 International (CC BY-NC 4.0). Read more
\n\nPeer Review Policies
\n\nAll scientific works are Peer Reviewed prior to publishing. Read more
\n\nOA Publishing Fees
\n\nThe Open Access publishing model employed by IntechOpen eliminates subscription charges and pay-per-view fees, enabling readers to access research at no cost. In order to sustain operations and keep our publications freely accessible we levy an Open Access Publishing Fee for manuscripts, which helps us cover the costs of editorial work and the production of books. Read more
\n\nDigital Archiving Policy
\n\nIntechOpen is committed to ensuring the long-term preservation and the availability of all scholarly research we publish. We employ a variety of means to enable us to deliver on our commitments to the scientific community. Apart from preservation by the Croatian National Library (for publications prior to April 18, 2018) and the British Library (for publications after April 18, 2018), our entire catalogue is preserved in the CLOCKSS archive.
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I am also a member of the team in charge for the supervision of Ph.D. students in the fields of development of silicon based planar waveguide sensor devices, study of inelastic electron tunnelling in planar tunnelling nanostructures for sensing applications and development of organotellurium(IV) compounds for semiconductor applications. I am a specialist in data analysis techniques and nanosurface structure. I have served as the editor for many books, been a member of the editorial board in science journals, have published many papers and hold many patents.",institutionString:null,institution:{name:"Sheffield Hallam University",country:{name:"United Kingdom"}}},{id:"54525",title:"Prof.",name:"Abdul Latif",middleName:null,surname:"Ahmad",slug:"abdul-latif-ahmad",fullName:"Abdul Latif Ahmad",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"20567",title:"Prof.",name:"Ado",middleName:null,surname:"Jorio",slug:"ado-jorio",fullName:"Ado Jorio",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"Universidade Federal de Minas Gerais",country:{name:"Brazil"}}},{id:"47940",title:"Dr.",name:"Alberto",middleName:null,surname:"Mantovani",slug:"alberto-mantovani",fullName:"Alberto Mantovani",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"12392",title:"Mr.",name:"Alex",middleName:null,surname:"Lazinica",slug:"alex-lazinica",fullName:"Alex Lazinica",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/12392/images/7282_n.png",biography:"Alex Lazinica is the founder and CEO of IntechOpen. After obtaining a Master's degree in Mechanical Engineering, he continued his PhD studies in Robotics at the Vienna University of Technology. Here he worked as a robotic researcher with the university's Intelligent Manufacturing Systems Group as well as a guest researcher at various European universities, including the Swiss Federal Institute of Technology Lausanne (EPFL). During this time he published more than 20 scientific papers, gave presentations, served as a reviewer for major robotic journals and conferences and most importantly he co-founded and built the International Journal of Advanced Robotic Systems- world's first Open Access journal in the field of robotics. Starting this journal was a pivotal point in his career, since it was a pathway to founding IntechOpen - Open Access publisher focused on addressing academic researchers needs. Alex is a personification of IntechOpen key values being trusted, open and entrepreneurial. Today his focus is on defining the growth and development strategy for the company.",institutionString:null,institution:{name:"TU Wien",country:{name:"Austria"}}},{id:"19816",title:"Prof.",name:"Alexander",middleName:null,surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/19816/images/1607_n.jpg",biography:"Alexander I. Kokorin: born: 1947, Moscow; DSc., PhD; Principal Research Fellow (Research Professor) of Department of Kinetics and Catalysis, N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow.\r\nArea of research interests: physical chemistry of complex-organized molecular and nanosized systems, including polymer-metal complexes; the surface of doped oxide semiconductors. He is an expert in structural, absorptive, catalytic and photocatalytic properties, in structural organization and dynamic features of ionic liquids, in magnetic interactions between paramagnetic centers. The author or co-author of 3 books, over 200 articles and reviews in scientific journals and books. He is an actual member of the International EPR/ESR Society, European Society on Quantum Solar Energy Conversion, Moscow House of Scientists, of the Board of Moscow Physical Society.",institutionString:null,institution:{name:"Semenov Institute of Chemical Physics",country:{name:"Russia"}}},{id:"62389",title:"PhD.",name:"Ali Demir",middleName:null,surname:"Sezer",slug:"ali-demir-sezer",fullName:"Ali Demir Sezer",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/62389/images/3413_n.jpg",biography:"Dr. Ali Demir Sezer has a Ph.D. from Pharmaceutical Biotechnology at the Faculty of Pharmacy, University of Marmara (Turkey). He is the member of many Pharmaceutical Associations and acts as a reviewer of scientific journals and European projects under different research areas such as: drug delivery systems, nanotechnology and pharmaceutical biotechnology. Dr. Sezer is the author of many scientific publications in peer-reviewed journals and poster communications. Focus of his research activity is drug delivery, physico-chemical characterization and biological evaluation of biopolymers micro and nanoparticles as modified drug delivery system, and colloidal drug carriers (liposomes, nanoparticles etc.).",institutionString:null,institution:{name:"Marmara University",country:{name:"Turkey"}}},{id:"61051",title:"Prof.",name:"Andrea",middleName:null,surname:"Natale",slug:"andrea-natale",fullName:"Andrea Natale",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"100762",title:"Prof.",name:"Andrea",middleName:null,surname:"Natale",slug:"andrea-natale",fullName:"Andrea Natale",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"St David's Medical Center",country:{name:"United States of America"}}},{id:"107416",title:"Dr.",name:"Andrea",middleName:null,surname:"Natale",slug:"andrea-natale",fullName:"Andrea Natale",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"Texas Cardiac Arrhythmia",country:{name:"United States of America"}}},{id:"64434",title:"Dr.",name:"Angkoon",middleName:null,surname:"Phinyomark",slug:"angkoon-phinyomark",fullName:"Angkoon Phinyomark",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/64434/images/2619_n.jpg",biography:"My name is Angkoon Phinyomark. I received a B.Eng. degree in Computer Engineering with First Class Honors in 2008 from Prince of Songkla University, Songkhla, Thailand, where I received a Ph.D. degree in Electrical Engineering. My research interests are primarily in the area of biomedical signal processing and classification notably EMG (electromyography signal), EOG (electrooculography signal), and EEG (electroencephalography signal), image analysis notably breast cancer analysis and optical coherence tomography, and rehabilitation engineering. I became a student member of IEEE in 2008. During October 2011-March 2012, I had worked at School of Computer Science and Electronic Engineering, University of Essex, Colchester, Essex, United Kingdom. In addition, during a B.Eng. I had been a visiting research student at Faculty of Computer Science, University of Murcia, Murcia, Spain for three months.\n\nI have published over 40 papers during 5 years in refereed journals, books, and conference proceedings in the areas of electro-physiological signals processing and classification, notably EMG and EOG signals, fractal analysis, wavelet analysis, texture analysis, feature extraction and machine learning algorithms, and assistive and rehabilitative devices. I have several computer programming language certificates, i.e. Sun Certified Programmer for the Java 2 Platform 1.4 (SCJP), Microsoft Certified Professional Developer, Web Developer (MCPD), Microsoft Certified Technology Specialist, .NET Framework 2.0 Web (MCTS). I am a Reviewer for several refereed journals and international conferences, such as IEEE Transactions on Biomedical Engineering, IEEE Transactions on Industrial Electronics, Optic Letters, Measurement Science Review, and also a member of the International Advisory Committee for 2012 IEEE Business Engineering and Industrial Applications and 2012 IEEE Symposium on Business, Engineering and Industrial Applications.",institutionString:null,institution:{name:"Joseph Fourier University",country:{name:"France"}}},{id:"55578",title:"Dr.",name:"Antonio",middleName:null,surname:"Jurado-Navas",slug:"antonio-jurado-navas",fullName:"Antonio Jurado-Navas",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/55578/images/4574_n.png",biography:"Antonio Jurado-Navas received the M.S. degree (2002) and the Ph.D. degree (2009) in Telecommunication Engineering, both from the University of Málaga (Spain). He first worked as a consultant at Vodafone-Spain. 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