\r\n\tThis book aims to explore the issues around the rheology of polymers, with an emphasis on biopolymers as well as the modification of polymers using reactive extrusion.
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He has 20 years experience in waste and by-product valorisation with an emphasis on renewable materials and biological products. Since his tertiary studies, Johan’s knowledge in the engineering field of sustainable products has led to a number of innovative developments in the engineering industry. 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\n
1. Introduction
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Chagas disease, also known as American trypanosomiasis, is caused by infection with the hemoflagellate protozoa Trypanosoma cruzi. This disease was first described in 1909, by the epidemiologist Carlos Justiniano Chagas. In this pioneering work, not only the etiological agent Trypanosoma cruzi was described, but also its evolutionary forms, life cycle, epidemiology and clinical manifestations of the disease was fully reported [1]. More than a century after this discovery, it is estimated that Chagas disease still affects around 6–7 million people worldwide, especially in Latin America, with more than 10,000 deaths annually [2]. Currently, Chagas Disease is considered as a neglected tropical disease by the World Health Organization [3].
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The progression of Chagas disease is characterized by the occurrence of three phases: acute, indeterminate and chronic. Survival during the acute phase of infection requires an inflammatory response involving cells of innate immunity, such as macrophages, dendritic cells and natural killers whereas in the chronic phase the T-lymphocyte-mediated immunity maintains parasite replication under control [4]. However, evidence suggests that the exacerbated inflammatory response of the host is one of the most determinant factors in the progression of Chagas disease, along with the virulence and tropism of the strain [5, 6].
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During T. cruzi infection—as in other infections—the immune system acts to protect the host from infectious agents and the nutrient status is an important factor contributing to immune response [7]. Between the components from the diet, fatty acids found in oils and oily food have an important role not only in the structure of cell membranes, energy source or as hormones precursors [8], but acts directly as modulators of the immune response [9]. Specifically, the consumption of fatty acids from the family of omega-3 polyunsaturated fatty acids (n-3 PUFAs), found in large amounts in fish oil, has been associated with anti-inflammatory and immunomodulatory effects [10]. Taking this into account, an important issue to be raised is the effect of n-3 PUFAs supplementation on infectious diseases, such as Chagas disease, where an efficient—but controlled inflammation—is necessary and important for host defense [11].
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Currently, daily oral supplementation with n-3 PUFAs is recommended by the American College of Cardiology and American Heart Association as an important adjuvant in the treatment of heart failure [12]. In the same sense, daily oral supplementation with n-3 PUFAs is recommended by the Brazilian Directive on Dyslipidemias and Prevention of Atherosclerosis, updated in 2017 by the Brazilian Society of Cardiology (2–4 g daily), as an important complement in the prevention of atherosclerosis and its cardioprotective benefits [13]. Despite the recognized relevance of n-3 PUFA supplementation in the supplementary treatment of cardiovascular diseases, and considering the important cardiac compromises that may occur during the chronic phase of Chagas disease, supplementation with n-3 PUFAs may in fact represent a perspective for the additional treatment of patients affected by Chagas disease. However, the immunomodulatory effects of the dietary supplementation with n-3 PUFAs and the relationship with the host response and resistance to T. cruzi infection should be carefully considered.
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2. Polyunsaturated fatty acids
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Polyunsaturated fatty acids (PUFAs) are a class of fatty acids with 18–22 carbons (C18–C22) containing two or more double bonds in the carbon chain. The most important PUFAs for human health and nutrition are the omega-6 (n-6) and omega-3 (n-3) families. The classification of the fatty acids between this families is made considering the position of the first double bond counting from the methyl end of the fatty acid chain [14]. Linoleic acid (LA) is considered the parent fatty acid of the n–6 PUFAs family, while α-linolenic acid (ALA) is considered the parent fatty acid of the n–3 PUFAs family. Both LA and ALA cannot be made by humans or other mammals, thus they are considered essential fatty acids and have to be supplied in the diet [15].
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The n-6 PUFA LA (18:2n-6) could be found naturally the seeds of most plants except for cocoa, coconut, and palm. On its turn, the n-3 PUFA ALA (18:3n-3) is found in the seeds of flax, rape, chia, perilla, walnuts (and their vegetable oils) or even chloroplast of green leafy vegetables. In the body, both LA and ALA are metabolized to longer-chain fatty acids of 20 or 22 carbons [15, 16]. LA is metabolized to arachidonic acid (AA), a long chain n-6 PUFA (LC n-6 PUFA) whereas ALA is metabolized to eicosapentaenoic acid (EPA, 20:5n-3) and docosahexaenoic acid (DHA, 22:6n-3), a long chain n-3 PUFAs (LC n-3 PUFA). This reaction occurs through the actions of elongases enzymes, that increase the chain length; and desaturases enzymes, which add extra double bonds to the carboxyl end of the fatty acid, increasing the degree of unsaturation [17]. Humans and others mammalians could convert LA in AA; and ALA in EPA and DHA, however this process is slow.
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Although there is a competition between n-6 PUFAs and n-3 PUFAs for the desaturation enzymes, which prefer the ALA instead the LA, the Western diet provides higher amounts of LA than ALA, being the AA the main unsaturated long-chain fatty acid produced [18]. Therefore, the most efficient way to increase the amount of LC n-3 PUFAs in the body is through directly ingestion of primary sources EPA and DHA, as the seafood. The LC n-3 PUFAs are found in high amounts in most seafood, especially in oily fish, in the blubber and tissues of sea mammals like seals and whales or even in supplements like fish oils, cod liver oil, krill oil, algal oils and in pharmaceutical grade preparations [10].
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3. Immunomodulatory effects of long chain n-3 polyunsaturated fatty acids
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Experimental assays have shown that diet supplementation with LC n-3 PUFAs results in powerful anti-inflammatory and immunomodulatory activities in a range of diseases, such as autoimmune [19], inflammatory bowel disease [20], rheumatoid arthritis [21] and even infectious diseases [22, 23, 24, 25]. There are also clinical trials in human patients associating the use of supplements rich in LC n-3 PUFAs with the evolution of inflammatory diseases [26] and infections, such as sepsis [27]. Studies in patients with rheumatoid arthritis are those that present better results, with several tests showing reduction of symptoms, such as morning swelling, pain and stiffness [28].
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Inflammation is a fundamental component of the body response to infections or injuries that involves the interactions among many different cell types. The leucocytes are cells from immune system found in the peripheral blood and lymph tissue that actively participate in the inflammation, being specially involved in body defense and protection [29]. Typically, inflammation is transient, exerting a protective role in the body. However, when the inflammation does not end and the acute response become chronic, this uncontrolled response leads to more injury [29]. Therefore, inflammation is the pathological mechanism behind many chronic diseases, and that is why the immunomodulatory effects of LC n-3 PUFAs are considered to be potentially beneficial.
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Some mechanisms of the immune response modulation by LC n-3 PUFAs are already known, such as modification of function and composition of immune system cell membranes, change in the pattern of eicosanoids produced and in the cytokine profile, regulation of gene expression and proliferation of T lymphocytes [30]. The leukocyte membrane phospholipids from humans consuming a Western diet typically have 15–20% of AA, 0.5–1% of EPA and 2–3% of DHA. When fish oil rich in LC n-3 PUFAs are incorporated to the diet, increased amounts of EPA and DHA are incorporated in these phospholipids in a time and dose dependent fashion, and it is occurs at the expense of AA [31, 32]. These changes in membrane fatty acid composition subsequently modify the cell-membrane fluidity, production of eicosanoids and the formation of lipid rafts [17, 33].
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4. Long chain n-3 PUFAs and Trypanosoma cruzi infection
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Infection with T. cruzi causes a strong inflammatory reaction at the inoculation site and, later, in the myocardium [34]. Approximately one-third to one-half of patients with indeterminate disease will eventually develop chronic Chagas cardiomyopathy (CCC). CCC results from the combined effects of persistent parasitism, parasite-driven tissue inflammation, micro-vascular and neurogenic dysfunction, and autoimmune responses triggered by the T. cruzi-infection [34, 35].
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There are few studies on the effects of increased consumption of LC n-3 PUFAs rich foods as well as the long-term effects of LC n-3 PUFAs on inflammatory profile and clinical outcomes in CCC. Recently, a group of Brazilian researchers reported that patients aging >18 years, with a diagnosis of CCC, that received LC n-3 PUFAs capsules (1.8 g EPA and 1.2 g DHA) during an 8-week period, presented modifications in the lipid and inflammatory profile, demonstrated by a decrease in triglycerides and improvements on IL-10 concentration [36]. The same group had already supposed in 2013 that the anti-inflammatory action of LC n-3 PUFAs may have beneficial effects on chronic chagasic cardiomyopathy, and could be translate into a less severe progression of cardiomyopathy, with subsequent reduction in morbidity [37].
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In mice, the resistance to acute infection has been shown to be dependent on interferon IFN-γ that activates macrophages to produce nitric oxide (NO) and kill the obligate intracellular amastigote form of the parasite [38, 39, 40]. In addition, TNF-α provides a second signal stimulating NO production and anti-T. cruzi activity in IFN-γ-activated macrophages.
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TNF-α is a cytokine that appears rapidly after infections or lesions, playing a key role in fighting invasive pathogens. However, excessive TNF-α production is related to mortality and morbidity in sepsis [41], meningitis [42] and malaria [43]. Although many of the studies about TNF-α modulation by treatment with LC n-3 PUFAs indicate a suppressive effect on this cytokine production, there are studies reporting an increase in cytokines production by treatment with LC n-3 PUFAs. Increased TNF-α production was reported by macrophages stimulated in vitro with LPS [25]. Dietary supplementation with fish oil on experimental Klebsiella pneumoniae infection and in brain-infection by Plasmodium berghei led to increased ex vivo production of TNF-α and IL-1α by in vitro LPS-stimulated macrophages [24]. Also, the in vivo treatment with fish oil increased TNF-α plasma levels in mice infected with Listeria monocytogenes in the first 24 hours of infection, being lower in later times [44]. In addition, specifically in T. cruzi infected-mice that were supplemented with fish oil rich in LC n-3 PUFAs it was related increased TNF-α production by the spleen cells [22].
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The first work on the in vivo effects of PUFAs supplementation on T. cruzi infection was published in 1958 by Godfrey and coworkers. They showed that oral supplementation with cod liver oil, rich in LC n-3 PUFA, associated with vitamins A and D, suppressed mice infections with T. congolense and T. vivax, but showed no effect on mice infected with T. cruzi or T. brucei [45]. However, when vitamin E was used together with cod liver oil, these adverse effects on host resistance on T. congolense and T. vivax infection were reversed, suggesting that diet-induced oxidative stress and vitamin E deficiency were central to this particular diet-infection relationship.
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In 1995, Takeda and collaborators reported that daily oral administration of the LC n-3 PUFA EPA, present in great amounts in fish oil, greatly diminished host survival following an experimental infection with T. cruzi [46]. As in the work of 1958, they included vitamin E in EPA treatment, in order to try to avoid the oxidative stress problem. The authors reported that their EPA-treatment failed to impact tissue parasitism, but was associated with elevated capacity to produce the inflammatory cytokine TNF-α.
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In contrast, more recently our research group has described that oral supplementation with fish oil on T. cruzi infected-mice did not change the mortality rate, but it did alter the course of parasitemia, as well as other important host responses, such the increased TNF-α production [22]. In T. cruzi infected-mice that were supplemented with fish oil rich in LC n-3 PUFAs we observed a transient, but substantial, increase in peak circulating parasitic load at the 7th day post infection. At the 12th day post infection, these fish oil-treated mice had similar levels of parasitemia in the blood compared to controls groups (mice treated with saline or corn oil). Surprisingly, besides de high peak of parasitemia, the mice that were treated with fish oil rich in LC n-3 PUFAs showed significantly fewer parasites in their cardiac tissue at the 12th day post infection (Figure 1) compared to mice treated with saline or corn oil. The oral supplementation with corn oil was used an alternative fat source rich in the n-6 PUFA linoleic acid but poor in LC n-3 PUFAs [22].
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Figure 1.
Effects of FO supplementation on cardiac parasitism. From 15 days before T. cruzi infection until the 12th day post infection, C57BL/6 mice were supplemented by gavage with 0.6% (v/w) saline, corn oil, or menhaden fish oil. C57BL/6 mice were infected with 5 × 103 blood trypomastigotes T. cruzi (Y strain). Cardiac parasitism (A): three heart sections were counted for each animal, and the results are expressed as means ± SEM of three sections from five animals per group and are representative of two independent experiments. Cardiac tissues (B) were examined by hematoxylin and eosin staining from uninfected mice (1) on day 12 after T. cruzi infection (2 and 3). Original magnifications were 400× (1 and 2) and 1000× (3). Original publication [22].
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In humans, as in some experimental animals, T. cruzi infection is associated with anemia, thrombocytopenia, leukopenia and bone marrow hypoplasia [47, 48, 49, 50]. Dietary supplementation with fish oil had no effect on the anemia of T. cruzi-infected mice [22], a finding that contrasts with the improvement in malaria-induced anemia reported by the treatment with LC n-3 PUFAs [46]. However, thrombocytopenia and leukopenia were less severe in T. cruzi-infected mice orally treated with fish oil [22].
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The production of eicosanoids represents an important role in the regulation between the host’s immune response and the establishment of T. cruzi infection (Figure 2A). Eicosanoids are lipid mediators of inflammation which include prostaglandins (PG), thromboxanes (TX), leukotrienes (LT) and lipoxins (LX). The initial substrate for the synthesis of eicosanoids is the lipids present in the membrane phospholipids of cells involved with inflammatory processes. In individuals with a regular western diet, AA is the most prevalent fatty acid in the inflammatory cell membrane, and it is usually the main substrate for the synthesis of eicosanoids, giving rise to series 2-series prostaglandins and thromboxanes and 4-series leukotrienes and lipoxins [30].
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Figure 2.
Mechanism and effects of PUFAs n-3 PUFAs supplementation on Trypanosoma cruzi infection. 1—The traditional western diet provides to immune cells great amounts of n-6 PUFAs arachidonic acid and linoleic acid, while a diet supplementation with LC n-3 PUFAs results in eicosapentaenoic acid and docosahexaenoic acid incorporation into immune cells plasma membrane phospholipids [31, 32]. 2—T. cruzi infection trigger inflammatory stimulus, as the expression of cyclooxygenase (COX) and Lipoxygenase (LOX) enzymes [53, 55]. The enzyme phospholipase A2 (PLA2) removes fatty acids from the membrane phospholipids, mainly arachidonic acid (AA) in cells from western diet and mainly eicosapentaenoic acid (EPA) or docosahexaenoic acid (DHA) from n-3 diet. 3—The enzymes COX and LOX uses the free fatty acids for eicosanoids synthesis. When AA is used as substrate 2-series prostaglandins/thromboxanes and 4-series leukotrienes/lipoxins are formed. When the substrate is EPA or DHA, a switch in the class of eicosanoids produced occurs, being produced 3-series prostaglandins/thromboxanes and 5-series leukotrienes/lipoxins [30], as well mediators that act in the resolution of inflammation: E-series resolvins generated from EPA, D-series resolvins from DHA, and protectins and maresins from DHA [72, 73]. 4—In the acute phase of infection, the high production of prostaglandin E2 (PGE2) leads to a transient immunosuppression, with decreased TNF-α production by the host [57]. The immune cells from n-3 diet produce lower amounts of PGE2, and consequently more TNF-α [22]. 5—The thromboxane A2 (TXA2) produced during T. cruzi infection is associated with a control mechanism of parasite proliferation and less exposure to immune system [67]. The decreased TXA2 production that occurs in cells from n-3 PUFAs diet could explain the increased parasitemia that were previously observed in vivo, leading to more T. cruzi exposition to immune system [22]. 6—Effects of in vivo supplementation of experimental mice during acute T. cruzi infection [22]. 7—Effects of in vivo supplementation of human patients with chronic Chagas cardiomyopathy [37]. Original publication [22].
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Acute T. cruzi infection in murine models is characterized by cardiac lesions associated by high levels of PGE2 [51]. During acute T. cruzi infection, both PGE2 and its EP-2 receptor are involved in inflammation and cardiac inflammatory infiltrate [52], as leukotrienes, that is important for the local production of NO and cardiac parasitism control [53, 54]. Additionally, plasma PGE2, TBX2 e 6-oxo-PGF1α levels are increased in murine models of acute infection [55, 56]. In addition to cardiac effects, PG are associated with immunosuppression of infected animals, with reduction in lymphocyte proliferation, on TNF-α levels, and in the microbicidal functions of macrophages [57, 58].
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In vitro assays have shown that the phagocytosis of apoptotic cells by macrophages during T. cruzi infection potentiates the release of PGE2 and transforming growth factor-beta (TGF-β) by these cells. These macrophages become refractory to inflammatory cytokines, consequently decreasing NO production and allowing parasite survival and growth even in an immune response environment [59]. Also, the pharmacological inhibition of the COX enzyme with aspirin in macrophages decreased the trypomastigotes internalization in these cells, with increase of interleukin-1 (IL1-β), NO and lipoxins [60]. In addition, PGE2 elicits signaling pathways capable of instantaneously inhibiting NLRP3 inflammation activation [61]. This may be relevant in the context of T. cruzi infection, since the activation of the inflammatory complex NLPR3 and caspase-1 is important for parasite control during the acute phase of infection, leading to activation of trypanocidal activities in macrophages, as NO production [62].
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Although PGE2 is important for the parasite survival at the beginning of infection, the in vivo pharmacological blockade of COX enzymes during the acute phase of T. cruzi infection leads to higher levels of parasitemia, lower survival rates of experimental mice and increased cardiac parasitism [63, 64, 65]. However, COX blockade with aspirin already in the chronic phase (60 days after infection) does not cause an increase in parasitemia or mortality, but is associated with an improvement in the cardiac ejection fraction [64].
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Confirming the relevance of inflammatory-lipid mediators during T. cruzi infection is the fact that the parasite itself synthesizes prostaglandins and thromboxanes (TX) [66]. Infective stages of T. cruzi have the enzyme phospholipase A-1, important for the release of fatty acids (such as AA) from the membranes and for eicosanoid synthesis, as represented in Figure 2A. From AA, T. cruzi preferentially synthesizes TXA2, in addition to small amounts of PGE2α [67]. During acute infection, TXA2 produced by the parasite acts on the vascular endothelium creating an inflammatory phenotype, increasing the expression of adhesion molecules and directly participating in the parasitemia control and host survival. The absence of TXA2 receptor in infected-host cells leads to large cellular parasitism, when compared to cells that have the receptor. This indicates that T. cruzi has a self-regulated mechanism that controls its proliferation trough TXA2 [67]. The effects of both TXA2 produced by the parasite and the PGE2 produced by the host create an immunomodulatory environment that favors the survival of the host, an indispensable factor for the survival of the parasite and maintenance of the chronic phase of the infection [63, 67].
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When incorporated into cell plasma membrane, LC n-3 PUFAs competitively inhibit the formation of eicosanoids from AA by the enzymes cyclooxygenase (COX) and lipoxygenase (LOX), being produced, from the fatty acids EPA and DHA, 3-series prostaglandins and thromboxanes and 5-series leukotrienes and lipoxins. These eicosanoids produced from the EPA and DHA have less inflammatory activity [68, 69]. This effect occurs in part due to the reduction of AA available, but also due to a direct action of the EPA decreasing the activity and expression of the COX-2 enzyme, that is responsible for the synthesis of prostaglandins after an inflammatory stimulus [70].
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We have shown that fish oil supplementation decreased the production of PGE2 in mice uninfected (Figure 3A) and infected with T. cruzi (Figure 3B) [22], as also represented in Figure 2B. In addition, as discussed above, it is reported in the scientific literature that LC n-3 PUFA supplementation promotes the production of 3-series thromboxanes, rather than the production of 2-series thromboxanes, a lipid mediator described as important for the regulation and continuity of infection by T. cruzi [67]. The use of LC n-3 PUFAs to modulate the production of eicosanoids exhibit relevant differences when compared to the use of pharmacological inhibitors of COX isoforms. While pharmacological COX blockade results in a marked decrease in eicosanoid production, the LC n-3 PUFAs acts promoting a change in the class of eicosanoids produced, without, however, completely abolishing those produced from AA. In addition, the inflammatory pro-resolution lipid mediators resolvins, maresins and protectins produced from the LC n-3 PUFAs DHA and EPA could control the tissue injury resulting from the exacerbated activation of the immune response [30]. Pro-resolvins are a class of lipid mediators that act in the resolution of inflammation [71]. E-series resolvins (RvE) are generated from EPA, D-series resolvins (RvD) from DHA, and protectins and maresins from DHA. The synthesis of these pro-resolvins also involves the COX and LOX pathway [72, 73].
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Figure 3.
Effects of fish oil supplementation on production of PGE2 by spleen cells from mice infected with T. cruzi. From 15 days before T. cruzi infection to the 7th dpi, C57BL/6 mice were supplemented by gavage with 0.6% (v/w) PBS, corn oil, or fish oil. C57BL/6 mice were infected with 5 × 103 blood trypomastigotes T. cruzi (Y strain). Splenocytes (5 × 106 cells/well) from uninfected (A) or T. cruzi-infected mice (B) were cultured with and without T. cruzi antigen (Tc-Ag). Supernatants were harvested after 8 hours, and PGE2 was quantified in supernatants by EIA. The results are expressed as means ± SEM from four animals per group and are representative of two independent experiments. Means not sharing letter are significantly different (P<0.05, 2-way ANOVA with Bonferroni post-test). Original publication [22].
\n
Recently was demonstrated that trypomastigotes and amastigotes of T. cruzi produce the pro-resolving lipids RvD1, RvD5, and RvE2. It has been reported that plasma RvD1 levels are elevated in T. cruzi infected mice and, at least in part, it is possible that this RVD1 is from the parasite itself. This mechanism suggests another way of how the parasite can modulate the environment in its favor. This modulation of the immune response by the parasite may be important and contribute to the perpetuation of the infection into the chronic phase [74].
\n
Therefore, the elucidation of the more specific mechanisms involved with the protective effects of n-3 PUFAs on T. cruzi infection (Figure 2C) are important aspects to be investigated. Considering the discussion presented here, as well as all points raised in the scientific literature, it is a reasonable to consider that the immune modulation exerted by LC n-3 PUFAs supplementation actually favors the host and may represent a perspective for the supplementary treatment of patients affected by Chagas disease.
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\n
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5. Conclusion
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The immunomodulatory effects of long-chain omega-3 polyunsaturated fatty acids (LC n-3 PUFA) are currently widely known. Dietary supplementation with LC n-3 PUFAs has been used as a complementary treatment in inflammatory diseases. However, the effects of daily supplementation with LC n-3 PUFAS on host resistance to infectious disease, such as the T. cruzi infection, are still poorly understood. Studies using a well-established mouse model of this human disease showed that fish oil supplementation improves de clinical course T. cruzi infection during the acute phase of infection. In fact, the potential benefits of LC n-3 PUFAs supplementation in humans have been the subject of recent clinical trials. The modulation of the immune response by LC n-3 PUFAs, mainly through the change in eicosanoids patterns produced during T. cruzi infection, could be one mechanism that results in improvement of the host response. However, more studies are necessary to determine whether or not oral supplementation with LC n-3 PUFA could benefit humans diagnosed with Chagas disease.
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Acknowledgments
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Funding: This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior-Brasil (CAPES) Finance Code 001, CNPq (grant Edital Universal 14-2014, research fellowships for PP-F (CNPq 307787/2015-0), MM-P (CNPq 307544/2016-8) and MILM (PNPD-Capes 22921091) and Fundação Araucária (grant 419-2009).
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Conflict of interest
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The authors declare that there are no conflicts of interest.
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Notes/thanks/other declarations
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This study would have been impossible without the aid and support of Dr. Kevin Fritsche Department of Nutrition and Exercise Physiology, University of Missouri, Columbia, 65,211, Missouri, USA.
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\n',keywords:"Trypanosoma cruzi, Chagas disease, n-3 PUFAs, dietary fish oil, disease control",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/66022.pdf",chapterXML:"https://mts.intechopen.com/source/xml/66022.xml",downloadPdfUrl:"/chapter/pdf-download/66022",previewPdfUrl:"/chapter/pdf-preview/66022",totalDownloads:365,totalViews:0,totalCrossrefCites:1,totalDimensionsCites:1,hasAltmetrics:0,dateSubmitted:"September 16th 2018",dateReviewed:"January 29th 2019",datePrePublished:"March 27th 2019",datePublished:"December 18th 2019",dateFinished:null,readingETA:"0",abstract:"Parasitic diseases constitute a big problem of ill health in both the tropics and subtropics as well as in more temperate climates and have been targeted by the Centers for Disease Control and Prevention (CDC) as priorities for public health in the USA. Parasitic infections can be caused by three types of organisms: protozoa, helminths and ectoparasites. They subsist on the host’s nutrients at the host’s expense. Effectively combating infections caused by parasites is essential for the survival of the organism. In this effort, cells and molecules of the immune system are susceptible to the modulating influence of fatty acids. The primary purpose of this chapter is to present a critical review of the multiple effects of fish-oil on Trypanosoma infection.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/66022",risUrl:"/chapter/ris/66022",book:{slug:"biology-of-em-trypanosoma-cruzi-em-"},signatures:"Maria Isabel Lovo-Martins, Marli Cardoso Martins-Pinge and Phileno Pinge-Filho",authors:[{id:"275285",title:"Associate Prof.",name:"Phileno",middleName:null,surname:"Pinge-Filho",fullName:"Phileno Pinge-Filho",slug:"phileno-pinge-filho",email:"pingefilho@uel.br",position:null,institution:null},{id:"287883",title:"Dr.",name:"Maria Isabel",middleName:null,surname:"Lovo-Martins",fullName:"Maria Isabel Lovo-Martins",slug:"maria-isabel-lovo-martins",email:"isabel.lovo@hotmail.com",position:null,institution:null},{id:"287884",title:"Dr.",name:"Marli Cardoso",middleName:null,surname:"Martins-Pinge",fullName:"Marli Cardoso Martins-Pinge",slug:"marli-cardoso-martins-pinge",email:"martinspinge@uel.br",position:null,institution:null}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Polyunsaturated fatty acids",level:"1"},{id:"sec_3",title:"3. Immunomodulatory effects of long chain n-3 polyunsaturated fatty acids",level:"1"},{id:"sec_4",title:"4. Long chain n-3 PUFAs and Trypanosoma cruzi infection",level:"1"},{id:"sec_5",title:"5. Conclusion",level:"1"},{id:"sec_6",title:"Acknowledgments",level:"1"},{id:"sec_6",title:"Conflict of interest",level:"1"},{id:"sec_7",title:"Notes/thanks/other declarations",level:"1"}],chapterReferences:[{id:"B1",body:'Chagas C. Nova tripanozomiaze humana: estudos sobre a morfolojia e o ciclo evolutivo do Schizotrypanum cruzi n. gen., n. sp., ajente etiolojico de nova entidade morbida do homem. Memórias do Instituto Oswaldo Cruz. 1909;1:159-218'},{id:"B2",body:'WHO. Chagas Disease (American Trypanosomiasis); 2017. Available from: http://www.who.int/mediacentre/factsheets/fs340/en/'},{id:"B3",body:'WHO. Why are Some Tropical Diseases called “neglected”? 2012. 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DOI: 10.1038/nature13479'},{id:"B72",body:'Hong S, Gronert K, Devchand PR, Moussignac RL, Serhan CN. Novel docosatrienes and 17S-resolvins generated from docosahexaenoic acid in murine brain, human blood, and glial cells. Autacoids in anti-inflammation. The Journal of Biological Chemistry. 2003;278(17):14677-14687. DOI: 10.1074/jbc.M300218200'},{id:"B73",body:'Mas E, Croft KD, Zahra P, Barden A, Mori TA. Resolvins D1, D2, and other mediators of self-limited resolution of inflammation in human blood following n-3 fatty acid supplementation. Clinical Chemistry. 2012;58(10):1476-1484. DOI: 10.1373/clinchem.2012.190199'},{id:"B74",body:'Colas RA, Ashton AW. Trypanosoma cruzi produces the specialized proresolving mediators resolvin D1, resolvin D5, and resolvin E2. Infection and Immunity. 2018;86(4):e00688. DOI: 10.1128/iai.00688-17'}],footnotes:[],contributors:[{corresp:null,contributorFullName:"Maria Isabel Lovo-Martins",address:null,affiliation:'
Department of Pathological Sciences, Laboratory of Experimental Immunopathology, Biological Sciences Center, State University of Londrina, Brazil
Department of Pathological Sciences, Laboratory of Experimental Immunopathology, Biological Sciences Center, State University of Londrina, Brazil
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1. Introduction
Clogging of mold nozzles, also called submerged entry nozzles (SEN), disrupts the steel casting process, affecting the caster’s productivity. The nozzle clogging produces inconsistent flow and temperature variations, steel level fluctuations in the mold, impairment of steel quality, and the steel casting’s abrupt interruption. Clogging starts when solid compounds, mainly steel skull and non-metallic inclusions, are non-uniformly deposited at the inner nozzle wall, at some typical preferential zones characterized for neighboring dead flow conditions [1, 2, 3, 4, 5]. These inclusions have as primary sources: (1) The reaction between the dissolved oxygen with the deoxidizers [6, 7, 8, 9]; (2) re-oxidation in the tundish or the nozzle [10, 11]; and (3) the entrainment of slag or refractory particles [11, 12, 13, 14]. Researchers who have worked on the determination of inclusions sources and clogging recognize that the deposited inclusions at the nozzle wall are mainly alumina inclusions [7, 8, 9, 15, 16]. Steel re-oxidation occurs due to possible air aspiration under the flow control valves (slide gate) to maintain the entry flow to the molds [17, 18, 19]. Besides, regardless of the refractory nozzle composition (alumina-graphite, zirconia, and magnesia), the steel melt infiltrates the refractory and removes the protective surface [11, 20], allowing the entrapment of refractory particles and inclusion attachment at the nozzle wall.
The non-metallic inclusions come from the steelmaking process; several researchers have focused on studying the variables that induce the inclusion deposition at the inner nozzle wall producing the clogging phenomena [1, 11, 12, 13, 14, 16, 21, 22]. Steel chemistry and, in particular, steel grades containing titanium, like Ti-SULC, (Ti Stabilized Ultra-Low Carbon Steels), steels enhance the nozzle clogging due to the surface tension properties of this element in liquid steel [23, 24, 25]. The wetting of inclusions, rich in Ti oxide, assists in the clustering and compaction of particles. When the ratio Ti/Al is above a threshold, dictated by thermodynamics, the wettability of complex oxides of Ti and Al works intensifying the nozzle’s clogging under the presence of oxygen. This series of papers provides an insight into the clogging phenomena while casting these steel grades.
In the present chapter, the authors deal with the physical–chemical aspects of the nozzle-clogging problem by inclusions originated through the deoxidation reactions of steel. Hence, to understand the fundamentals of the problem first, these particle’s nucleation and growth are considered using non-equilibrium thermodynamics principles. Second, the influence of the steel refining processes on the deoxidation particle morphology and the relation with their further growth through aggregation and clustering mechanisms is under scrutiny. The analysis continues with studying the thermodynamics related to the oxide particle’s adherence to the refractory. Finally, a dynamic analysis lets the establishment of balance among drag, buoyancy, adherence, and lift forces leading to a detachment criterion for an inclusion forming part of a first layer of the clogging. After this work, conclusions and recommendations are provided.
2. Non-equilibrium thermodynamics
2.1 Nucleation and growth rates of oxide inclusions
The nucleation of a foreign phase in an originally homogeneous solution, in the present case an oxide particle in a liquid solution of iron, is driven by the free energy of the reaction.
xM+yO=MxOyE1
∆Gm=∆Gm0+RTlnaMxOyhMxhOy=∆Gm0+RTlnQE2
where Q is the activity quotient, in the thermodynamic equilibrium ∆Gm=0 and the Eq. (2) changes to,
∆Gm0=−RTlnKEE3
where KE is the equilibrium constant, which depends only on the temperature. Combining Eqs. (2) and (3), dividing the result between the molar volume of the oxide results in,
∆GV=RTlnQKE=−RTlnS0V0E4
and S0 is the supersaturation ratio given by,
S0=QKE=KMOKE=hMxhOyhMxhOyE=%Mx%Oy%Mx%OyEE5
KMO is the solubility product of the oxide. The free energy balance for the nucleation of an oxide precipitated in the homogeneous melt includes the volumetric free energy and the surface energy opposing to the stabilization and growth of the nucleus,
∆G=4πr2σPL+43πr3∆GVE6
Making zero the derivative of the free energy (Table 1 [26, 27] reports the molar Gibbs free energy of deoxidation reactions of iron melts) allows the calculation of the critical radius for the onwards growth of the nucleus, obtaining,
where kB = 1.38X10−23 J K−1, is the Boltzmann constant, A = 1032 m−3 s−1 is the frequency factor, VO is the oxide’s molar volume, σPL is the interfacial tension between liquid iron and an oxide particle, R is the gas constant, and T is temperature. The critical supersaturation SO* is the minimum one to nucleate one nucleus m−3 s1. Hence, making I = 1 m−3 s−1 in Eq. (9) implies SO*=S0, and gives,
S0=expV0RT16πσPL33kBTlnAE11
The supersaturation of iron melts in contact with different oxides was measured through electrochemical methods [29]. The critical supersaturation, SO*, depends on the oxide’s nature and surface tension, as seen in the precedent equation. The experimental results provide the inclusions sizes’ statistical dispersion directly in the sense that the larger surface tensions, contributing to the opposing free surface energy to the nucleation, lead to larger size dispersions [26]. Table 2 shows the experimental results of supersaturation experiments reported in Ref. [26] using different metal deoxidizers. The second and third columns are the molar volume and the interfacial tension between the oxide and the melt, the fourth and fifth, the experimental and calculated critical supersaturations through Eq. (11). The sixth and seventh columns include the experimental and corrected supersaturations, respectively. Revision of these data shows that the magnitudes of the calculated critical supersaturations are larger than the experimental critical supersaturations. The other observations are the small magnitudes of the experimental supersaturation. The large differences behind the critical supersaturations are due to the experimental data’s nature as they correspond to the metal bulk property. On the other hand, the other magnitude (the corrected supersaturations) is theoretically related to the nuclei’s curvature, as is schematized in Figure 1. The curvature raises the gradients of concentration of all solutes, M (Al, Si, Mn, Mg, Ti, Zr, Ca) and O in the nuclei’s tip and, consequently, the critical supersaturations are larger in the proximities of the tip than in the metal bulk. The curvature, given by rC−1 is calculated through Eq. (7) and matching its magnitude by considering an embryo formed by two or three pairs of M-O dimers, (consulting for that purpose the atomic radius of the involved elements of the corresponding oxides in the Periodic Table).
OXIDE
Vo [m3. Mol−1]
σPL[J. m2]
S*O (exp.)
S*O (cal.)
SO
S*O (exp.) corr
SO corr.
MgO
1.10E-05
1.8
8.4
280
3.6 ∼ 7.2e4
280.224
1801440
ZrO2
1.01E-05
1.63
4.5
85
48 ∼ 68
84.825
1093.3
Al2O3
8.60E-06
2.11
14.7
529
37 ∼ 60
530.229
1803.5
CaO
1.65E-05
1.17
3.4
83
CaO-Al2O3
1.47E-05
1.3
3.6
92
8.5E+04
90.936
2147100
SiO2
1.13E-05
1.24
1
27
MnO-SiO2
1.36E-05
1
1.7
18
1.5
18.598
16.41
Table 2.
Experimental, calculated and corrected critical supersaturation degree for precipitation of oxides [26].
Figure 1.
Supersaturations of alumina close and far away from surfaces with finite and infinite curvature radius.
The correction of the experimental supersaturations is possible through the Gibbs–Thomson’s Equation which gives the ratio between both types of supersaturations as,
S0,corrr=r=SO,expr=∞expV0RT2σrcE12
The nucleation process consumes short times of the order of microseconds [26, 29, 30], as shown schematically by Figure 2. The fluctuations of concentrations in the liquid structure, after the de-oxidant addition, require a critical supersaturation reached in the point (a) of this figure. Once reached the critical supersaturation, the embryo starts with a group of M-O dimers that develop into metastable structures becoming into a nuclei, and as the thermodynamic and kinetic conditions permit it, evolves in alumina with time, as seen in Figure 3. After stabilizing the nuclei, the local supersaturation decreases by diffusion process [31], due to the local consumption of M and O, to the point (b) in Figure 2 where the nucleation kinetics overlaps with the diffusion process. The supersaturation continues decreasing and the diffusion overlaps with the particle growth through the Ostwald ripening process summarized by the following expression [32],
Figure 2.
Evolution of supersaturations with time during nucleation and initial growths by diffusion and Ostwald ripening mechanisms.
Figure 3.
Nucleation of an alumina lattice from the union of Al-O dimers.
r´3−r´03=αkdtE13
kd=2σDOVOCORTCP−COE14
where CO and CP are the concentrations of dissolved oxygen and oxygen content in the oxide, respectively, and DO is the diffusion coefficient of oxygen. Further growth phenomena of the particles, in industrial vessels, includes Stokes collisions, collisions among particles driven by turbulent flows deriving in aggregates of particles and clusters. Grown particles are easily floated out thanks to the bottom stirring with argon of steel ladles which carries these particles through their contact with gas bubbles, and melt convection making them contact the slag facilitating their absorption in this phase.
Figure 4a and b show the effect of the supersaturation on the nucleation kinetics on the nucleation rates of different oxides recalculated from reference [26]. There are two important differences, the first is that the nucleation rates are considerably lower than those reported in Ref. [26] and the second is the larger supersaturations required to precipitate the MgO shown in Figure 4b. Another important feature is the small supersaturations required for the precipitation of silica and manganese silicate. Therefore, those particles requiring small or relatively small supersaturations yield the largest nucleation rates meaning, physically, the fast generation of million of nuclei distributed inside the reaction and diffusion boundaries. The main obstacle of a particle to born is the creation of a new surface preceding the formation of a small volume in a hosting matrix, as is seen in Figure 3, with a different structure. Those particles requiring larger supersaturations would, eventually, nucleate smaller populations of particles with a broader size distribution once their first step of development ends. The precipitates characterized by high and low supersaturations are schematized in Figure 5a and b, respectively, showing the period for each one of them. The first case will yield numerous small particles with limited growth as the supersaturation decays providing a narrow size distribution. The longer times lead to larger diffusion and growth time scales yielding broader size distributions in the second case. The time scales change to exponentially larger ones when the precipitates of solid-state transformations take place. For example, steel aging by nitrogen diffusion consumes long times as the diffusion coefficients of this interstitial element are very small in ferrite or austenite phases at 300°C [32, 33] compared with its diffusion coefficient at 1600°C [34], as is schematized in Figure 5c and d. Hence, the interfacial tension between the melt and the nuclei governs the nucleation rate, as seen in Figure 6. Alumina has one of the lowest nucleation rates as its interfacial tension is large, and its crystals will have a broad spectrum of sizes after the nucleation and the diffusion end.
Figure 4.
Effect of supersaturation ratios on nucleation rate at 1600°C, (a) various metal deoxidizers, (b) with magnesium.
Figure 5.
Schematics of nucleation rate evolution with time. (a) High nucleation rates at low supersaturation in liquid state, (b) high nucleation rates in solid state, (c) low nucleation rates at high supersaturation in liquid state, (d) low nucleation rates in solid state.
Figure 6.
Nucleation rate as a function of surface tension between the particle and the melt at 1600°C.
2.2 Alumina morphology
Alumina may acquire a wide diversity of morphologies depending on the concentrations of oxygen and the deoxidant. Accordingly, the initial supersaturation ratio influences the morphology of alumina. Figure 7 shows a scheme of the relation between oxygen concentrations and the deoxidant with the particle morphology [35]. In oxidized melts, the inclusions are rounded spheroids, as the oxygen activity decreases the surface roughness develops reaching the stage of dendritic precipitation. With further deoxidation the morphology changes to faceted, disks and crystalline rhomboids.
Figure 7.
Evolution of the growth shapes of oxide inclusions as a function of the local oxygen activity (solid line) and deoxidizer activity (dashed line) according to Steinmetz [35].
The heterogeneous nucleation of alumina particle also yields characteristic morphologies. Other foreign particles catalyze alumina’s nucleation in the melt, such as those of metastable iron oxide precipitated in the steelmaking furnace and manganese silicates in the refining ladle [36]. A catalyzed nucleation process means that the foreign particle decreases the supersaturation required by the precipitation process of the particle through a decrease of the free energy according to [32],
∆Ghet=−43πr3∆Gv+4πr2σPLSθE15
where
Sθ=2+cosθ1−cosθ24E16
Note that except for factor S(θ) this expression is the same as that obtained for homogeneous nucleation, Eq. (6). S(θ) has a numerical value ≤1 dependent only on θ, i.e. contact angle and the nucleus’s shape. A catalyzed alumina particle will have a morphology depending on the oxide’s nature over which it nucleates as shown in Figure 8 [36]. If the foreign o catalyzer particle is a silicate, already existent given its high nucleation rate, a chemical reaction intervenes,
Figure 8.
Heterogeneous nucleation of alumina on iron oxide and silicate particles [36].
2Al+MnO∙SiO2=Al2O3+Mn+SiE17
if the particle is iron oxide, then
2Al+3FeO=Al2O3+3FeE18
The interfacial tension between the alumina and silicate particles is reduced due to the chemical reaction, a layer of alumina, (it is initially nucleated and the alumina layer grows by the reaction), surrounds the particle of silicate making sluggish the diffusion of aluminum through the alumina layer to continue the reaction. During the process, some particles of Mn and Si precipitate as products of the reaction (17). No dendrites were observed and there is the presence of needle like clusters with disk type terminations indicating a growth under small supersaturations, once the oxygen content decreases. Iron oxide suffers a rapid reduction by aluminum, reaction (18) and the product is an alumina particle without other phases. Other alumina particles nucleate heterogeneously on the original alumina particles and yield dendritic morphologies.
2.3 Further growth of inclusions
After concluding the nucleation and growth by diffusion and Ostwald ripening, the inclusions continue their growth through direct collision. In a Stokes flow regime, the probability for collision among inclusions of sizes R1 and R2 is [37],
ws=29g∆ρμR1−R2R1+R23E19
and the probability of collision under the action of turbulent eddies is expressed by the Saffman’s Equation as [38],
In Stokes regime, the highest collision probability is observed when the inclusions have large size differences as seen in Figures 9 and 10 indicates that collisions of silicate inclusions smaller than ten μm, have low probabilities for collisions under turbulent flow conditions and those with large dimensions have higher collision probabilities. Figure 11 shows the corresponding collision probabilities for alumina inclusions and particles as small as three μm yield the highest probabilities for a collision. Therefore, alumina inclusions grow from microscopic inclusions to large aggregates and clusters by collisions among small particles forming aggregates [40]. Roughly speaking, in the turbulence regions, in a bottom stirred ladle, the ratio between Stokes and Safmann’s regimes is approximately 6X104. Thereby, deoxidation during steel tapping in bottom stirred ladles is the most indicated step to deoxidize and grow inclusions by turbulent collisions. This is particularly applicable to the growth of alumina particles. Indeed, vigorously stirred melts at tapping times, lead to cleaner steel heats [41]. In the secondary refining of steel, where the turbulence levels are considerably smaller, this ratio decreases and is the highest in the argon-plume regions, while in the top layer of the bath, the Stokes regime dominates.
Figure 9.
Comparison of the collision probability (Stoke’s model) with the radius of the inclusions. Miki Y, Kitaoka H, Sakuraya T, Fujii T. mechanism for separating inclusions from molten steel stirred with a rotating electro-magnetic field. ISIJ Int. 1992;32:142–149. DOI: 10.2355/isijinternational.32.142. Reproduced with permission [39].
Figure 10.
Comparison of the collision probability (Saffman’s model) with the radius of the inclusions. Miki Y, Kitaoka H, Sakuraya T, Fujii T. mechanism for separating inclusions from molten steel stirred with a rotating electro-magnetic field. ISIJ Int. 1992;32:142–149. DOI: 10.2355/isijinternational.32.142. Reproduced with permission [39].
Figure 11.
Prediction of the collision probability (Saffman’s model) for alumina inclusions. Miki Y, Kitaoka H, Sakuraya T, Fujii T. mechanism for separating inclusions from molten steel stirred with a rotating electro-magnetic field. ISIJ Int. 1992;32:142–149. DOI: 10.2355/isijinternational.32.142. Reproduced with permission [39].
2.4 Bond strength among particles
Another important aspect of inclusions growth is the stability of aggregates and clusters, forming large particles that float out of the bath faster as larger are their sizes. Strong bond strengths are desirable as once the particles form aggregates or clusters, their integrity must prevail, avoiding the generation of smaller particles, by breaking processes due to turbulence, which may bring on floatation slowness. The variety of bonds among inclusions with a wide spectrum of morphologies is simplified into three basic cases, sphere-sphere, sphere-plate and plate-plate, see Figure 12. According to thermodynamic calculations of surface tensions, the plate-plate geometry yields the largest bond strength, as suggested by Figure 13 [42]. The bond strength, eventually, will increase by the thickenings of the neck formed by the union of two particles of alumina through diffusion processes according to,
Figure 12.
Geometries of the gas cavity of different contact types [42].
Figure 13.
Attractive force for different contact types. Zheng L, Malfliet a, Wollants P, Blanpain B, Guo M. effect of alumina morphology on the clustering of alumina inclusions in molten iron. ISIJ Int. 2016;56:926–935. DOI: 10.2355/isijinternational.ISIJINT-2015-561. Reproduced with permission [42].
x5R2=K1σPPV0RTDVtE21
In this equation, DV = 1.3X10exp−110000RT [43], σpp=1Jm2 is the interfacial tension between alumina particles K1 = 10–100 [43]. Figure 14 shows the mechanism of diffusion of vacancies in the alumina lattice to form the bond [44]. The bond strength reaches the order of MPa due to the interdiffusion between alumina particles [45].
Figure 14.
Models for initial stages of sintering of spherical particles showing the vacancies diffusion paths [43].
3. Adherence of alumina particles on refractory surfaces
The adhesion of alumina inclusions to the refractory surface has its highest repercussion in the nozzle feeding with liquid steel the continuous casting slab mold. The property governing these phenomena is the contact angle between a particle and a solid phase with a smooth surface as is shown in Figure 15, which is a function of the surface tension and known as Young’s law [47],
Figure 15.
Contact angle between surfaces in a liquid in equilibrium with a vapor phase [46].
σSL=σSV−σLVcosθYE22
In actual refractory materials, there are not smooth surfaces and have certain levels of asperities and roughness. Hence, Eq. (22) suffers a modification through a roughness factor, r, to become in the Wenzel’s Equation [47],
cosθW=rcosθYE23
A further modification includes the consideration of the heterogeneous structural nature of industrial materials such as refractories for continuous casting and Eq. (23) becomes into the Cassie-Baxter Equation [47],
θCB=∑i=1nfnσi,SV−σi,SLσLVE24
Where the limits i and n, in Eq. (24), corresponding to the stable phases forming part of the refractory material and fi is the surface fraction of phase i. The following conditions establish the wettability conditions: when σSV>σSL,00<θCB<900, the liquid wets the solid. When σSL>σSV,900<θCB<1800, the solid and the liquid have a poor wettability. The work of adhesion between a particle and a substrate is derived from Young’s Equation,
Wad=σSV+σLV−σSL=σLV1+cosθCBE25
A specific case of changes of surface tension of liquid steel is the case of ultra-low carbon steels stabilized with Ti (Ti-SULC steels) where this element decreases this property as seen in Figure 16a, and the work of adhesion as a function of the Ti content is shown in Figure 16b [46]. This effect of Ti on the surface tension of Ti-SULC steels enhances the wettability between the melt and the inclusions. The wettability of hydrophilic and hydrophobic systems (such as steelmaking and casting processes) increases and decreases, respectively, with surface roughness, leaving behind the ideal behavior, indicated by Young’s Equation, as the best condition. Figure 17a shows the effects of the surface roughness on the contact angle or Wenzel angle. Increasing the roughness ratios make a hydrophilic system more hydrophilic and a hydrophobic system in a more hydrophobic one. It can be assumed that in the actual metal-refractory contact, due to poor wettability between the two phases, a gas can be trapped in between the asperities of the surface, such that the liquid sits on a surface having a distribution of solid asperities and gas pockets (two-component surface material) and their surface fractions are fS and fV respectively, where fS+fV=1. Substituting in the CB Equation for the solid–liquid fraction f1=fS and cosθCB.1=cosθCB,2 and the gas pocket fraction f2 = fV and cosθCB,2=−1 because the fraction is completely dry (no-wetting) and combining the roughness ratio factor r with the CB Equation, we get
Figure 16.
Interfacial properties between liquid steel containing Ti and alumina particles, (a) interfacial tension, (b) adhesion work. González-Solórzano M.G., Morales R.D. Gutiérrez E, Guarneros J, Chattopadhyay K. analysis of fluid flow of liquid steel through clogged nozzles: Thermodynamics analysis and flow simulation. Steel. Res. Int. 2020;91. DOI: 10.1002/srin.202000049. Reproduced with permission [46].
Figure 17.
Effect of roughness and voids on the surface refractory on interfacial properties, (a) comparison between Wenzel’s and Young’s equation, (b) effect of solid fraction for contact points according to the Cassie-Baxter equation. Of fluid flow of liquid steel through clogged nozzles: thermodynamics analysis and flow simulation. Steel. Res. Int. 2020;91. DOI: 10.1002/srin.202000049. Reproduced with permission [46].
cosθapp=rfScosθCB+fS−1E26
The examination of Eq. (26) indicates that if the fraction fS approaches 0, by increasing the asperities of the surface, there will be a condition of perfect non-wettability. This trend is shown in Figure 17b. On the contrary, if fS approaches 1 (complete surface smoothness), the contact angle is given by Eq. (26) with r = 1. The combined effects of roughness and a solid fraction are as follows: in a hydrophilic system, the simultaneous increases of solid fraction and surface roughness make a hydrophilic system more hydrophilic. A decrease of the solid fraction with a combined increase of surface roughness makes this hydrophobic system in a more hydrophobic one. Decreasing the adherence of inclusions on the refractory surface requires two simultaneous conditions that must be fulfilled: a small contact angle between the melt and the inclusion and a low contact angle between the refractory and the melt. Therefore, to manipulate the second angle, there may be two ways:
The first is to use CaO as a surface cover, which would be wetted it by liquifying the alumina inclusions and decreasing the contact angle between the melt and the calcium aluminate inclusion.
Use a conventional AG material with a special treatment leading to smooth surfaces according to the results presented in Figure 17.
The changes of wettability among the refractory, the melt, and the inclusions are summarized in Figure 18(a–d):
The contact angle 1 (between the inclusion and the melt) is larger than the contact angle 2 (between the refractory and the melt). Hence, the liquid does not wet the nozzle. Therefore, the refractory rejects the metal, and there is the adhesion of the inclusion to the wall.
When the contact angle 2 is larger than angle 1, the nozzle is slightly wettable by the melt and allows that this one enters between the inclusion and the wall, making a small separation between them and reducing the strength of adhesion.
When angle 2 decreases further, the nozzle wall will increase its wettability by the melt. Hence, the separation between the inclusion and the wall becomes larger, making inclusion separate from the nozzle wall.
In this case, the liquid wets the inclusion; if the inclusion is liquid, it will go with the flow, but if it is solid, the inclusion approaches the wall and will remain adhered to it.
Figure 18.
Effects of melt-refractory and melt-inclusion contact angles on particle-refractory surface adhesion.
As the liquid steel flows through the nozzle, Figure 19, the alumina particles are transported along, and those close to the boundary layer might, eventually, get in this region and adhere to the refractory’s surface by mechanisms of fluctuating velocities [48, 49]. Therefore, in current casting systems, the adherence of an alumina particle to the surface of a nozzle refractory is favored by the low wettability of the inclusion and the refractory by the melt.
Figure 19.
Adhesion of alumina clusters and aggregates contained in the liquid flow on the nozzle surface.
3.1 Adherence force
When a particle approaches the solid surface or to another particle, both unwetted by the liquid, the formation of a cavity between them becomes thermodynamically favorable, see Figure 20. This phenomenon is because the replacement of a particle-liquid interface by a particle-vapor interface leads to a negative change of the Gibbs free energy according to Young’s Equation. Once the cavity is formed, an attractive force of adhesions develops, FA, as expressed in the following Equation [50],
Figure 20.
Schematization of a cavity between a sphere and a plate in a non-wetting system.
FA=2πσLVl+πl2∆PE27
The cavity might be filled with: (1) gaseous components initially dissolved in the melt (2) gaseous components coming from the refractory (3) melt vapor, or (4) liquid phases forming due to a local rise in the oxygen concentration. In any case, there will be a pressure drop between the liquid outside of the cavity and the phase inside of it. The pressure difference obeys Laplace’s Eq. (45),
∆P=σLV1r−1lE28
Where l and r are the principal radii of the cavity. The two parameters determine the profile of the liquid–vapor interface, which can be either optimized using the Laplace-Young Equation at constant pressure drop or approximately described with a piece of a circle with radius r. When the cavity is in equilibrium with the liquid phase, its shape is determined by thermodynamics. The estimated adhesion force between an alumina particle and the wall of an AG (alumina-graphite nozzle) is about 25X10−6 N [51], large enough to keep fixed the particle on the refractory surface.
4. Boundary conditions of wall adhesion
To design nozzle materials through the principles of physical-chemistry of interfaces and techniques of computer fluid dynamics, reliable boundary conditions for inclusion adherence to the refractory wall are necessary. In other words, to develop new materials is necessary to deal with a theoretical analysis including effects of surface roughness, the effect of impurities in alumina graphite materials (mainly Na2O and K2O, oxides cover) together with control of the boundary layer by the internal design of the nozzle [46] before making investments on experimental research. Specifically, this boundary condition is applicable only during the development of the clog’s first layer and not during its growth. That is to say, when the first layer of the clog stabilizes, its future growth is guaranteed by contact with other alumina particles, which will go through a sinterization process by diffusion of vacancies, as explained above, forming high strength bonds. This boundary condition is derived from a balance of forces, according to Figure 21. These forces obey the following expressions [52]:
Different force ratios working on the particles are useful as possible boundary conditions or, simply, to compare the magnitudes of these forces as follows:
Ratio for the vertical lift-off
Rv=FLFaE33
Ratio for the sliding:
Rs=Fd+FbksFa−FLE34
Ratio for the tangential lift-off:
Rt=1.4rpFd+aFL+rpFbaFaE35
The constants and variables included in these expressions are reported in Table 3 [53]. In these calculations, instead of using Eq. (30) to estimate the adhesion force, the force suggested of 25X10−6 N was employed [51]. This force was calculated by optimizing Eq. (27) and Eq. (28) and is considered a more realistic magnitude. The force ratios calculated for a ten μm particle in a liquid steel flow are in the last column of Table 3. Some conclusions derived from these results are a) The lift force is negligible compared with the adhesion force. b) The ratio for sliding is small compared with the effects of the adhesion force. c) Summing the momentums of drag, lift, and buoyancy forces and compared with the adhesion force’s momentum yields a magnitude larger than one, meaning that the particle may be dislodged from the wall.
Parameters and constants to estimate the forces on a particle with a 10 μm diameter.
Closure
The clogging phenomena have their roots in the deoxidation step of the liquid steel. Operational factors like the addition time of aluminum, oxygen supersaturation, temperature, and melt stirring fixe the initial conditions of sizes distributions and the alumina particle’s population responsible of the nozzle clogging. The high level of supersaturation required by aluminum governs the initial size distribution. Once the particle is nucleated at the initial stages, the initial growth is through diffusion and Ostwald ripening mechanisms. Although not proved yet here, the published literature reports that the bond strength among alumina particles and their morphology are important on the clogging mechanism. Once inside the nozzle, the particle, taking contact with refractory, may remain adhered to it if the adhesion force is larger than the momentums originated from the lift, buoyancy and drag forces with the particle size.
The refractory’s roughness is of no help to control the clogging as those materials that are hydrophobic or hydrophilic will enhance these properties with rough surfaces. Ideally, a smooth surface approaching the Young’s Law would be the ideal material to decrease clogging. Raw materials purity is of interest as some oxides are easily reduced by the carbon of the nozzle or aluminum in the melt, all working to enhance the clogging problem.
Under the present situation, this work contributes to the understanding of the surface phenomena in the areas of inclusion nucleation and growth of inclusions and the steel refining and the interaction with the refractory. It gives options for the boundary conditions applied in computational fluid dynamics simulations, all focused on designing new nozzle materials.
Nomenclature
CO
Oxygen concentration in the melt
CP
Oxygen concentration in the oxide
dp
Particle diameter
DO
Diffusion coefficient of oxygen in the melt
DV
Coefficient diffusion of vacancies
f
Correction factor
F
Force
Fs, Fv
Surface fraction of solid and vapor phase, respectively
g
Gravity constant
hi
Henryan activity of i
I
Nucleation rate
kB
Boltzmann’s constant
l
Principal radii
No
Constant
P
Pressure
r
Inclusion radii
r0
Initial radii of the inclusion
rc
Critical nuclei radii
R
Gas constant and particle radii
R1
Particle 1 radii
R2
Particle 2 radii
S0
Supersaturation
t
Time
T
Temperature
VO
Oxide molar volume
w
Collision probability of two particles in turbulent flow regime
Wad
Work of adhesion
Ws
Probability for collisions for two particles in Stokes’s regime
x
Neck radii
Greek letters
α
Accommodation factor
γ
Shear rate
ε
Dissipation rate of kinetic energy
θ
Contact angle
μ
Dynamic liquid viscosity
ν
Kinematic liquid viscosity
ρ
Density
σ
Surface tension
Sub indexes
a
Adhesion
app
Apparent
b
Buoyancy
c
critical
CB
Cassie-Baxter
d
Drag
het
Heterogeneous
L
Lift
LV
Liquid–Vapor
M
Metal
O
Oxide
PL
Particle-Liquid
SL
Solid–Liquid
SV
Solid-Vapor
v
Molar volume
w
Wenzel
y
Young
\n',keywords:"steel deoxidation, nozzle clogging, melt supersaturation, nucleation, growth, interfacial tension",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/74692.pdf",chapterXML:"https://mts.intechopen.com/source/xml/74692.xml",downloadPdfUrl:"/chapter/pdf-download/74692",previewPdfUrl:"/chapter/pdf-preview/74692",totalDownloads:82,totalViews:0,totalCrossrefCites:0,dateSubmitted:"July 17th 2020",dateReviewed:"December 4th 2020",datePrePublished:"January 12th 2021",datePublished:"February 24th 2021",dateFinished:"January 5th 2021",readingETA:"0",abstract:"Nozzle clogging in continuous casting of steel originates by the adherence of alumina particles and other oxides, precipitated during the liquid steel deoxidation, on the refractory material’s surface. Hence, these particles’ nucleation and growth rates in supersaturated melts are analyzed considering, specifically, the role of the interfacial tensions between alumina, silica, and other oxides and the liquid metal. Weak steel deoxidizers like silicon do not need high supersaturations favoring high nucleation rates, giving particles’ narrow size distributions thanks to fast diffusion and Ostwald-ripening coagulation. Strong deoxidizers, like aluminum, need high supersaturation levels leading to broad size distributions. Besides, the morphology of these particles depends on the nucleation and growth mechanisms. The adhesion forces among the deoxidation particles, forming clusters, depending on the morphology and the oxide’s chemistry. The stability of the nozzle’s clog, adhered to the nozzle’s wall, depends on the interface tensions between the melt and the nozzle’s refractory surface and between the melt and the inclusion. The results obtained here help set up basic recommendations in steel refining and materials specifications of casting nozzles.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/74692",risUrl:"/chapter/ris/74692",signatures:"María-Guadalupe González Solórzano, Rodolfo Morales-Dávila, Jafeth Rodríguez Ávila, Carlos Rodrigo Muñiz-Valdés and Alfonso Nájera Bastida",book:{id:"10432",title:"Casting Processes and Modelling of Metallic Materials",subtitle:null,fullTitle:"Casting Processes and Modelling of Metallic Materials",slug:"casting-processes-and-modelling-of-metallic-materials",publishedDate:"February 24th 2021",bookSignature:"Zakaria Abdallah and Nada Aldoumani",coverURL:"https://cdn.intechopen.com/books/images_new/10432.jpg",licenceType:"CC BY 3.0",editedByType:"Edited by",editors:[{id:"201670",title:"Dr.",name:"Zak",middleName:null,surname:"Abdallah",slug:"zak-abdallah",fullName:"Zak Abdallah"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}},authors:[{id:"106163",title:"Dr.",name:"Rodolfo",middleName:null,surname:"Morales",fullName:"Rodolfo Morales",slug:"rodolfo-morales",email:"rmorales@ipn.mx",position:null,institution:{name:"Instituto Politécnico Nacional",institutionURL:null,country:{name:"Mexico"}}},{id:"241727",title:"Dr.",name:"Carlos-Rodrigo",middleName:null,surname:"Muñiz-Valdez",fullName:"Carlos-Rodrigo Muñiz-Valdez",slug:"carlos-rodrigo-muniz-valdez",email:"rodrigo.muniz@uadec.edu.mx",position:null,institution:null},{id:"337015",title:"Ms.",name:"Maria Guadalupe",middleName:null,surname:"González-Solórzano",fullName:"Maria Guadalupe González-Solórzano",slug:"maria-guadalupe-gonzalez-solorzano",email:"maria_gs09@hotmail.com",position:null,institution:{name:"Instituto Politécnico Nacional",institutionURL:null,country:{name:"Mexico"}}},{id:"342255",title:"Dr.",name:"Jafeth",middleName:null,surname:"Rodríguez Ávila",fullName:"Jafeth Rodríguez Ávila",slug:"jafeth-rodriguez-avila",email:"drjafethra@gmail.com",position:null,institution:null},{id:"342256",title:"Dr.",name:"Alfonso Nájera",middleName:null,surname:"Bastida",fullName:"Alfonso Nájera Bastida",slug:"alfonso-najera-bastida",email:"alfonso_najera@yahoo.com.mx",position:null,institution:null}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Non-equilibrium thermodynamics",level:"1"},{id:"sec_2_2",title:"2.1 Nucleation and growth rates of oxide inclusions",level:"2"},{id:"sec_3_2",title:"2.2 Alumina morphology",level:"2"},{id:"sec_4_2",title:"2.3 Further growth of inclusions",level:"2"},{id:"sec_5_2",title:"2.4 Bond strength among particles",level:"2"},{id:"sec_7",title:"3. Adherence of alumina particles on refractory surfaces",level:"1"},{id:"sec_7_2",title:"3.1 Adherence force",level:"2"},{id:"sec_9",title:"4. Boundary conditions of wall adhesion",level:"1"},{id:"sec_12",title:"Nomenclature",level:"1"}],chapterReferences:[{id:"B1",body:'Long M., Zuo X., Zhang L., Chen D., Kinetic modeling on nozzle clogging during steel billet continuous casting. ISIJ Int. 2010;50:712–720. 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DOI: 10.1007/s11663-019-01551-x'},{id:"B23",body:'Lee J.H., Kang Y.B., Growth of initial clog deposits during continuous casting of Ti-ULC steel formation and reduction of the initial deposits at nozzle/steel interface. ISIJ Int. 2020;60:426–435. DOI: 10.2355/isijinternational.ISIJINT-2019-384'},{id:"B24",body:'Lee J.H., Kang M.H., Kim S.K., Kang Y.B., Oxidation of Ti added ULC steel by CO gas simulating interfacial reaction between the steel and SEN during continuous casting. ISIJ Int. 2018;58:1257–1266. DOI: 10.2355/isijinternational.ISIJINT-2018-164'},{id:"B25",body:'Lee J.H., Kang M.H., Kim S.K,. Kim J., Kim M.S., Kang Y.B., Influence of Al/Ti ratio in Ti-ULC steel and refractory components of submerged entry nozzle on formation of clogging deposits. ISIJ Int. 2019;59:749–758. DOI: 10.2355/isijinternational.ISIJINT-2018-672'},{id:"B26",body:'Suito H., Ohta H., Characteristics of particle size distribution in early stage of deoxidation, ISIJ Int. 2006;46:33–41. 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F!uid Mech. 1956;1:16–30'},{id:"B39",body:'Miki Y., Kitaoka H., Sakuraya T., Fujii T., Mechanism for separating inclusions from molten steel stirred with a rotating electro-magnetic field. ISIJ Int. 1992;32:142–149. DOI: 10.2355/isijinternational.32.142'},{id:"B40",body:'Dekkers R., Jokanovic N., Rombout A., Blanpain B., Wollants P., Steel cleanliness during secondary metallurgy of high-grade quality electric steels. Steel. Res. Int. 2005;76:475–480. DOI: 10.1002/srin.200506042'},{id:"B41",body:'Delgado M., SIMEC Operations, private communication, Steelmaking Manager, SIMEC Group, Special Steels Plant. Tlaxcala, Mexico, 2019'},{id:"B42",body:'Zheng L., Malfliet A., Wollants P., Blanpain B., Guo M., Effect of alumina morphology on the clustering of alumina inclusions in molten iron. ISIJ Int. 2016;56:926–935. DOI: 10.2355/isijinternational.ISIJINT-2015-561'},{id:"B43",body:'Ooi H., Sekine M., Kasai G., On the Mechanisms of alumina cluster formation in molten iron. Tetsu-to-Hanage 1973;59:1078–1088. DOI: 10.2355/tetsutohagane1955.59.8_1078'},{id:"B44",body:'Kingery W.D., Bowen H.K., Uhlmann D.R., Introduction to Ceramics. 2nd ed. Wiley; 1976. 474–475 p'},{id:"B45",body:'Kuczynski G.C., Selft-diffusion in sintering of metallic particles. Trans. Met. Soc. AIME 1949;185:169–178. DOI: 10.1007/978-94-009-0741-6_33'},{id:"B46",body:'González-Solórzano M.G., Morales R.D., Gutiérrez E., Guarneros J., Chattopadhyay K., Analysis of fluid flow of liquid steel through clogged nozzles: thermodynamics analysis and flow simulation. Steel. Res. Int. 2020;91. DOI: 10.1002/srin.202000049'},{id:"B47",body:'Eustathopoulos N., Nicholas M.G., Devrit B., Wettability at High Temperatures. 1st ed. Pergamon Press: Amsterdam; 1999. 1 p'},{id:"B48",body:'Suito H., Ohta H., Characteristics of particle size distribution in early stage of deoxidation. ISIJ Int. 2006;46:33–41. DOI: 10.2355/isijinternational.46.33'},{id:"B49",body:'Rashidi M., Hestroni G., Barnejee S., Particle-turbulence interaction in a boundary layer. Int. Journal of Multiph. Flow 1990;16:935–949. DOI: 10.1016/0301-9322(90)90099-5'},{id:"B50",body:'Simons S.J.R., Seville J.P.K., Adams M.J., Analysis of the rupture energy of pendular liquid bridges. Chem. Eng. Sci. 1994;49:2331–2339. DOI: 10.1016/0009-2509(94)E0050-Z'},{id:"B51",body:'Diéguez-Salgado U., Investigation of particle attraction by steel/refractory and steel/gas interfaces and the associated relevance for clogging in casting processes [thesis]. Leoben; University, Austria, 2018'},{id:"B52",body:'Liming Shi L., Bayless D., Comparison of boundary conditions for predicting the collection efficiency of cyclones Pow. Tech. 2007;173:29–37. DOI: 10.1016/j.powtec.2006.11.022'},{id:"B53",body:'Johnson K.L., Kendall K., Roberts A.D., Suface energy and the contact of elastic solids. In: Proceedings of the Royal Society A. 08 September 1971. p. 301–313. DOI: 10.1098/rspa.1971.0141'}],footnotes:[],contributors:[{corresp:null,contributorFullName:"María-Guadalupe González Solórzano",address:null,affiliation:'
Instituto Politécnico Nacional-ESIQIE, Department of Metallurgy, Mexico
Instituto Politécnico Nacional-UPIIZ, Metallurgical Engineering, Blvd. del Bote 202, Cerro del Gato, 98160, México
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IntechOpen Authors that wish to use this service will receive a 20% discount on all translation services. To find out more information or obtain a quote, please visit https://www.enago.com/intech
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SPi Global
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SPi Global is the market leader in technology-driven solutions for the extraction, enrichment and transformation of content assets. IntechOpen publishing services are designed to meet the unique needs of Authors. As part of our commitment to that objective, we have an ongoing partnership agreement for production solutions.
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Amazon
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Amazon is the world’s largest online retailer and cloud services provider. IntechOpen books have been available on Amazon since 2017, guaranteeing more visibility for our Authors and Academic Editors.
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DHL
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IntechOpen has partnered with DHL since 2011 to ensure the fastest delivery of Print on Demand books.
The Association of Learned and Professional Society Publishers (ALPSP) is the largest association of scholarly and professional publishers in the world. Its mission is to connect, inform, develop and represent the international scholarly and professional publishing community. IntechOpen has been a member of ALPSP since 2016 and has consequently stayed informed about industry trends through connecting with peers and developing jointly.
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OASPA
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The Open Access Scholarly Publishers Association (OASPA) was established in 2008 to represent the interests of Open Access (OA) publishers globally in all scientific, technical and scholarly disciplines. Its mission is carried out through exchange of information, the setting of standards, advancing models, advocacy, education, and the promotion of innovation.
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STM
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The International Association of Scientific, Technical and Medical Publishers (STM) is the leading global trade association for academic and professional publishers. As a member, IntechOpen has not only made a commitment to STM's Ethical Principles.
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COPE
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The Committee on Publication Ethics (COPE) provides advice to editors and publishers on all aspects of publication ethics and, in particular, how to handle cases of misconduct in research and publication. IntechOpen has been a member of COPE since 2013 and adheres to the COPE Code of Conduct and Best Practice Guidelines, ensuring that we maintain the highest ethical standards.
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Creative Commons
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Creative Commons (CC) is a nonprofit organization that enables the sharing and use of creativity and knowledge through free legal tools. IntechOpen uses the CC BY 3.0 license for chapters, meaning Authors retain copyright and their work can be reused and adapted as long as the source is properly cited and Authors are acknowledged.
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Crossref
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Crossref is the official Digital Object Identifier (DOI) Registration Agency for scholarly and professional publications with a goal of making scholarly communications more effective. IntechOpen deposits metadata and registers DOIs for all content using the Crossref System. IntechOpen also deposits its references and uses the Crossref Cited-by service that enables researchers to track citation statistics.
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Altmetric and Dimensions from Digital Science
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Digital Science is a technology company serving the needs of scientific and research communities at key points along the full cycle of research. They support innovative businesses and technologies that make all parts of the research process more open, efficient and effective. IntechOpen integrates tools such as Altmetric to enable our researchers to track and measure the activity around their academic research and Dimensions, to ease access to the most relevant information and better understand and analyze the global research landscape.
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CLOCKSS
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CLOCKSS preserves scholarly publications in original formats, ensuring that they always remain available and openly accessible to everyone.
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Counter
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COUNTER provides the Code of Practice that enables publishers and vendors to report usage of their electronic resources in a consistent way. This enables libraries to compare data received from different publishers and vendors.
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DORA
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DORA is a worldwide initiative covering all scholarly disciplines which recognizes the need to improve the ways in which the outputs of scholarly research are evaluated and seeks to develop and promote best practice. To date it has been signed by over 1500 organizations and around 14,700 individuals.
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iThenticate
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iThenticate is the leading provider of professional plagiarism detection and prevention technology and is used worldwide by scholarly publishers and research institutions to ensure the originality of written work before publication. IntechOpen uses the iThenticate plagiarism software to ensure content originality and the research integrity of our published work.
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Enago
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IntechOpen collaborates with Enago, through its sister brand, Ulatus, one of the world’s leading providers of book translation services. Their services are designed to convey the essence of your work to readers from across the globe in the language they understand.
\n\t
IntechOpen Authors that wish to use this service will receive a 20% discount on all translation services. To find out more information or obtain a quote, please visit https://www.enago.com/intech
\n
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SPi Global
\n\n
\n\t
SPi Global is the market leader in technology-driven solutions for the extraction, enrichment and transformation of content assets. IntechOpen publishing services are designed to meet the unique needs of Authors. As part of our commitment to that objective, we have an ongoing partnership agreement for production solutions.
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Amazon
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Amazon is the world’s largest online retailer and cloud services provider. IntechOpen books have been available on Amazon since 2017, guaranteeing more visibility for our Authors and Academic Editors.
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DHL
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IntechOpen has partnered with DHL since 2011 to ensure the fastest delivery of Print on Demand books.
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