Phylogenetic affiliation of sequences obtained from DGGE bands from water (W) and feces (F).
\\n\\n
Released this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\\n\\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
Note: Edited in March 2021
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'IntechOpen is proud to announce that 191 of our authors have made the Clarivate™ Highly Cited Researchers List for 2020, ranking them among the top 1% most-cited.
\n\nThroughout the years, the list has named a total of 261 IntechOpen authors as Highly Cited. Of those researchers, 69 have been featured on the list multiple times.
\n\n\n\nReleased this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\n\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
Note: Edited in March 2021
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The 13 chapters and preface of this book discuss other potential applications of magnetic spinels along with various methods used for their synthesis and their varied properties resulting from substituting different metal ions at the A and B sites. These applications include ferrofluids, anticorrosion coatings, absorber coatings for photothermal conversion, biomedicine, and environmental applications such as oxidation of volatile organic compounds and removal of arsenic and heavy metals from water. Emphasis is placed on structure-property correlations and on the nature of magnetism in spinels and their nanoparticles with current information provided for future research.",isbn:"978-953-51-2974-5",printIsbn:"978-953-51-2973-8",pdfIsbn:"978-953-51-4102-0",doi:"10.5772/63249",price:139,priceEur:155,priceUsd:179,slug:"magnetic-spinels-synthesis-properties-and-applications",numberOfPages:316,isOpenForSubmission:!1,hash:"c3c43611e3fb0a8ab988acc896eae935",bookSignature:"Mohindar Singh Seehra",publishedDate:"March 8th 2017",coverURL:"https://cdn.intechopen.com/books/images_new/5514.jpg",keywords:null,numberOfDownloads:21915,numberOfWosCitations:60,numberOfCrossrefCitations:29,numberOfDimensionsCitations:63,numberOfTotalCitations:152,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"May 9th 2016",dateEndSecondStepPublish:"May 30th 2016",dateEndThirdStepPublish:"September 3rd 2016",dateEndFourthStepPublish:"December 2nd 2016",dateEndFifthStepPublish:"January 1st 2017",remainingDaysToSecondStep:"5 years",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:"Edited by",kuFlag:!1,biosketch:null,coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"48086",title:"Prof.",name:"Mohindar",middleName:"Singh",surname:"Seehra",slug:"mohindar-seehra",fullName:"Mohindar Seehra",profilePictureURL:"https://mts.intechopen.com/storage/users/48086/images/system/48086.jpg",biography:"Professor Mohindar S. Seehra received his early education in India (B.Sc. Punjab University; M.Sc.: Aligarh University). He joined West Virginia University as Assistant Professor of Physics in 1969 after receiving Ph.D. (University of Rochester, USA), becoming Associate Professor in 1973, Professor in 1977 and Eberly Distinguished Professor in 1992. His honors in research include: A. P. Sloan Foundation Research Fellow (1974-1976); Fellow of the American Physical Society (1984-present); Fellow of the Institute of Physics, UK (2001-present); and Outstanding Referee Award of the American Physical Society in 2010. He has guided the research of 65 graduate and postdoctoral students and authored over 300 publications on the magnetic, dielectric, optical and catalytic properties of materials and nanoparticles and edited two books. 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by"}},{type:"book",id:"428",title:"Ferroelectrics",subtitle:"Characterization and Modeling",isOpenForSubmission:!1,hash:null,slug:"ferroelectrics-characterization-and-modeling",bookSignature:"Mickaël Lallart",coverURL:"https://cdn.intechopen.com/books/images_new/428.jpg",editedByType:"Edited by",editors:[{id:"10041",title:"Dr.",name:"Mickaël",surname:"Lallart",slug:"mickael-lallart",fullName:"Mickaël Lallart"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"429",title:"Ferroelectrics",subtitle:"Applications",isOpenForSubmission:!1,hash:null,slug:"ferroelectrics-applications",bookSignature:"Mickaël Lallart",coverURL:"https://cdn.intechopen.com/books/images_new/429.jpg",editedByType:"Edited by",editors:[{id:"10041",title:"Dr.",name:"Mickaël",surname:"Lallart",slug:"mickael-lallart",fullName:"Mickaël Lallart"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"6198",title:"Magnetism and Magnetic Materials",subtitle:null,isOpenForSubmission:!1,hash:"ccf0a4d8e8e42ef4e29f805286ab43f9",slug:"magnetism-and-magnetic-materials",bookSignature:"Neeraj Panwar",coverURL:"https://cdn.intechopen.com/books/images_new/6198.jpg",editedByType:"Edited by",editors:[{id:"289829",title:"Dr.",name:"Neeraj",surname:"Panwar",slug:"neeraj-panwar",fullName:"Neeraj Panwar"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"8653",title:"Electromagnetic Materials and Devices",subtitle:null,isOpenForSubmission:!1,hash:"0cc0489a203ae888b1105719a4e70ecd",slug:"electromagnetic-materials-and-devices",bookSignature:"Man-Gui Han",coverURL:"https://cdn.intechopen.com/books/images_new/8653.jpg",editedByType:"Edited by",editors:[{id:"250649",title:"Prof.",name:"Man-Gui",surname:"Han",slug:"man-gui-han",fullName:"Man-Gui Han"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"49561",title:"Water and Flamingo Feces Bacterial Communities from High- Altitude Andean Lakes under Selective Antibiotic Pressure Studied by PCR-DGGE Analyses",doi:"10.5772/61967",slug:"water-and-flamingo-feces-bacterial-communities-from-high-altitude-andean-lakes-under-selective-antib",body:'High-Altitude Andean Lakes (HAAL) are a system of shallow oligotrophic lakes originated in the tertiary age distributed across the
In this chapter, we compare bacterial diversity using Denaturant Gradient Gel Electrophoresis (DGGE) under antibiotic pressure conditions in water and flamingo feces from three HAAL: Laguna Aparejos, Laguna Negra, and Laguna Azul.
Aparejos, Negra, and Azul lakes are located in the Andes Mountains in the northwest of Argentina; their physic and chemical characteristics are described by Dib et al. [3]. They are a group of lakes and salar pads called Salar de la Laguna Verde in the Andean region of Catamarca province, Argentina (27º 34´ S; 68º 32´ W). Some of the highest mountains of the Andean system are located in this area: Ojos del Salado (6,885 m) and Nevado Pissis (6,779 m). The water temperature was 5ºC at the sampling time (1 pm local hour) and the maximal UV-B irradiance reached 3.3 Wm-2 for 312 nm (half band with 300–325 nm).
Two types of samples were considered: water and flamingo feces. Surface water samples were collected during summer 2009 (near the beginning of austral spring) in 10 L sterile polyethylene bottles. Water samples were stored at 4ºC until further processing in the laboratory (within 24 h after collection), which is located 600 km away from the sampling site. Flamingo feces were taken near the lake and conserved in sterile bags at 4ºC until processing. Once in a sterile environment in the lab, core feces samples were extracted for cultivation.
To determine bacterial diversity under selective pressure, water samples from Laguna Aparejos, Laguna Negra, Laguna Azul, and four flamingo feces samples from each lake were analyzed. Samples were inoculated in 20 mL of R2A medium (yeast extract 0.5 g L-1, peptone 0.5 g L-1, casamino acids 0.5 g L-1, glucose 0.5 g L-1, soluble starch 0.5 g L-1, sodium pyruvate 0.3 g L-1, K2HPO4 0.3 g L-1, MgSO4×7H2O 0.05 g L-1; pH 7.2), with different ATBs. Control cultures without ATBs were also performed. Five ATBs were used: ampicillin (Amp), 100 µg mL-1; chloramphenicol (Cm), 170 µg mL-1; colistin (Col), 20 µg mL-1; erythromycin (Ery), 50 µg mL-1; and tetracycline (Tet) 50 µg mL-1. After five days of incubation at 30ºC and 150 rpm, the cells were pelleted by centrifugation and total DNA was extracted from the ATB enriched cultures. Afterward, DGGE profiles of total community cultured without or with different ATBs were determined.
DNA extraction from total community cultures was performed using a CTAB method [16]. The variable V3 region of 16S rRNA gene was amplified by PCR [17]. The nucleotide sequences of the primers are as follows: primer 1 F341: 5’-CGC CCG CCG CGC CCC GCG CCC GTC CCG CCG CCC CCG CCC GCC TAC GGG AGG CAG CAG-3’, primer 2 R518: 5’-CGT ATT ACC GCG GCT GCT GG-3’, primer 3 F357: 5’-TTA CTG ATA GAA TGT GGA GC-3’[18].
PCR amplification was performed with a Biometra Termocycler as follows: 100 ηg of purified genomic DNA, 20 pmol of each primers (Genbiotech), 200 µmol of each deoxyribonucleoside triphosphate, 10 µL of 10× PCR buffer (MgCl2) and 0.25 U of Go Taq polymerase (Promega) were added to a 0.2 mL volume microtube, which was filled up to a volume of 25 µL with sterile Milli-Q-water. PCR was performed using the following conditions: initial denaturing step of 15 min at 95°C, followed by 30 cycles of 95°C for 1 min, 65°C for 1 min, and 72°C for 1 min 30 s. A touchdown program was performed in order to down one grade at each cycle, until 55ºC. At this last temperature, 15 additional cycles were programmed, with a final extension at 72°C for 5 min. DGGE was performed with the Bio-Rad Protean II system, essentially as described previously [19]. PCR products were applied directly onto 8% (wt/vol) polyacrylamide gels in 1X TAE buffer (40 mM Tris base, 20 mM sodium acetate, 1 mM EDTA) and a linear gradient consisting of the denaturants urea and formamide; the concentration of the denaturants increased from 40% at the top of the gel to 60% at the bottom. Electrophoresis was performed at a constant voltage of 120 V and a temperature of 60ºC during 5 h. After electrophoresis, the gel was stained for 10 min with SYBR® Gold (Molecular Probes, Eugene, OR), rinsed with TAE buffer, and visualized with a Bio-Rad UV Gel Doc 2000 transilluminator. Distinguishable bands were excised from the gel; the eluted DNA was reamplified using the primers 2 and 3, and PCR products were sequenced.
Fifty-nine selected 16S rRNA sequences from DGGE bands in this paper have been deposited in GenBank database under the following accession numbers: AM712052–66, AM711573–79, AM711878–90, and AM889064–87.
The similarity in DGGE bands in each lake was assessed by Cluster Analysis using the Jaccard’s index, applying the UPGMA (unweight pair-group method using averages) algorithm with software MVSP 3.2.
The affiliation of the prominent reamplified bands from DGGE gels from major bacterial community members obtained from ATB enrichment cultures, from water and feces, in all studied lakes is shown in Table 1. 16S rRNA gene sequence comparisons revealed that most of the water and feces DGGE bands were represented mainly by
Band sequences related to
In Laguna Aparejos, two bands sequences (A15 and A18) were exclusively recovered from water and they presented similarities with members of the genera
The sequence related to
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
\n\t\t\t\t | \n\t\t||||
\n\t\t\t\t | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t |
A16 | \n\t\t\t\n\t\t\t\t | \n\t\t\t90 | \n\t\t\tF, W | \n\t\t\tCol | \n\t\t
A18 | \n\t\t\t\n\t\t\t\t | \n\t\t\t98 | \n\t\t\tW | \n\t\t\tAmp | \n\t\t
\n\t\t\t\t | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t |
A1 | \n\t\t\t\n\t\t\t\t | \n\t\t\t100 | \n\t\t\tW, F | \n\t\t\tAmp, Col, Ery Cm, Tet | \n\t\t
A2; A3; A4A; A16a, A5A | \n\t\t\t\n\t\t\t\t | \n\t\t\t96-100 | \n\t\t\tW, F | \n\t\t\tAmp, Ery, Cm, Tet | \n\t\t
A9; A10; A14; A8A | \n\t\t\t\n\t\t\t\t | \n\t\t\t98-100 | \n\t\t\tW, F | \n\t\t\tAmp, Ery, Col, Tet | \n\t\t
A2A | \n\t\t\t\n\t\t\t\t | \n\t\t\t98 | \n\t\t\tF | \n\t\t\tAmp | \n\t\t
A13 | \n\t\t\t\n\t\t\t\t | \n\t\t\t95 | \n\t\t\tW, F | \n\t\t\tAmp, Ery | \n\t\t
A15 | \n\t\t\t\n\t\t\t\t | \n\t\t\t98 | \n\t\t\tW | \n\t\t\tAmp, Col, Tet | \n\t\t
A13a | \n\t\t\t\n\t\t\t\t | \n\t\t\t98 | \n\t\t\tF | \n\t\t\tAmp, Ery, Cm, Tet | \n\t\t
Firmicutes | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t |
A11a | \n\t\t\t\n\t\t\t\t | \n\t\t\t96 | \n\t\t\tF | \n\t\t\t\n\t\t |
A11 | \n\t\t\t\n\t\t\t\t | \n\t\t\t98 | \n\t\t\tF | \n\t\t\tCol | \n\t\t
A14a | \n\t\t\t\n\t\t\t\t | \n\t\t\t99 | \n\t\t\tF | \n\t\t\t\n\t\t |
A12a | \n\t\t\t\n\t\t\t\t | \n\t\t\t97 | \n\t\t\tF | \n\t\t\t\n\t\t |
\n\t\t\t\t | \n\t\t||||
\n\t\t\t\t | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t |
N1 | \n\t\t\t\n\t\t\t\t | \n\t\t\t97 | \n\t\t\tW, F | \n\t\t\tAmp, Col | \n\t\t
N2 | \n\t\t\t\n\t\t\t\t | \n\t\t\t99 | \n\t\t\tW, F | \n\t\t\tAmp, Col | \n\t\t
N8; N5 | \n\t\t\t\n\t\t\t\t | \n\t\t\t96-99 | \n\t\t\tF | \n\t\t\tAmp | \n\t\t
N10; N11; N11a; N12 | \n\t\t\t\n\t\t\t\t | \n\t\t\t99 | \n\t\t\tW, F | \n\t\t\tAmp, Col | \n\t\t
N13; N14 | \n\t\t\t\n\t\t\t\t | \n\t\t\t95-99 | \n\t\t\tW, F | \n\t\t\tAmp, Col, Tet | \n\t\t
N16; N19 | \n\t\t\t\n\t\t\t\t | \n\t\t\t99-100 | \n\t\t\tW | \n\t\t\tCol, Ery, Tet | \n\t\t
Firmicutes | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t |
N6 | \n\t\t\t\n\t\t\t\t | \n\t\t\t99 | \n\t\t\tF | \n\t\t\tAmp | \n\t\t
N9; N15 | \n\t\t\t\n\t\t\t\t | \n\t\t\t99-100 | \n\t\t\tF | \n\t\t\tAmp, Col | \n\t\t
\n\t\t\t\t | \n\t\t||||
\n\t\t\t\t | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t |
Az1; Az14 | \n\t\t\t\n\t\t\t\t | \n\t\t\t92-95 | \n\t\t\tW | \n\t\t\tAmp, Col, Tet | \n\t\t
\n\t\t\t\t | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t |
Az11 | \n\t\t\t\n\t\t\t\t | \n\t\t\t98 | \n\t\t\tF | \n\t\t\tCm, Tet | \n\t\t
Az9 | \n\t\t\t\n\t\t\t\t | \n\t\t\t99 | \n\t\t\tF | \n\t\t\tCol | \n\t\t
Az16; Az18 | \n\t\t\t\n\t\t\t\t | \n\t\t\t96 | \n\t\t\tF | \n\t\t\tCol, Tet | \n\t\t
\n\t\t\t\t | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t |
Az4 | \n\t\t\t\n\t\t\t\t | \n\t\t\t83 | \n\t\t\tW | \n\t\t\tCol | \n\t\t
Az19; Az20; Az2; | \n\t\t\t\n\t\t\t\t | \n\t\t\t96-99 | \n\t\t\tW, F | \n\t\t\tAmp | \n\t\t
Az6; Az15; Az10; Az21; Az8; Az25; Az23; Az7; Az17 | \n\t\t\t\n\t\t\t\t | \n\t\t\t96-99 | \n\t\t\tF | \n\t\t\tAmp, Ery, Tet | \n\t\t
Firmicutes | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t |
Az24 | \n\t\t\t\n\t\t\t\t | \n\t\t\t96 | \n\t\t\tF | \n\t\t\tEry | \n\t\t
Az13; Az12; Az3 | \n\t\t\t\n\t\t\t\t | \n\t\t\t98-100 | \n\t\t\tW, F | \n\t\t\tEry, Amp, Col | \n\t\t
Actinobacteria | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | \n\t\t |
Az5 | \n\t\t\t\n\t\t\t\t | \n\t\t\t96 | \n\t\t\tF | \n\t\t\t\n\t\t |
Phylogenetic affiliation of sequences obtained from DGGE bands from water (W) and feces (F).
The microbial diversity by DGGE in water and feces after cultivation under antimicrobial pressure could be explained by the presence of ATB-resistant traits or the acquisition of resistant traits by horizontal gene transfer events during cultivation.
In Laguna Aparejos, there was a band sequence detected in the five enrichment cultures conditions. It was the case of a band sequence related to
In Laguna Negra, most of the DGGE-detected bands were found in Col- and Amp-enriched cultures. Two band sequences (N13, N14) matched with
DGGE band sequences matched with
Figure 1 shows the dendrogram resulting from the Cluster Analysis performed among samples taking into account the presence or absence of individual bands obtained by DGGE profiles of Laguna Aparejos. The analysis evidenced that water and flamingo feces without any antimicrobial pressure clustered together conforming a subgroup.
Clustering using band-based Jaccard coefficient for Laguna Aparejos samples.
In Laguna Negra, cluster analysis indicates that water, feces, and feces with Amp clustered within the same subgroup (Figure 2).
UPGMA dendrogram resulting from the Cluster Analysis performed among samples from Laguna Negra.
In Laguna Azul, two clear groups can be observed, one for feces samples and the other for water samples (Figure 3).
Dendrogram based in Jaccard coefficient showing the similarity coefficient of bacterial community from enrichment ATBs cultures from water and flamingo feces.
It was proposed that landscape ecology, which links the biotic and abiotic factors of an ecosystem, might help to untangle the complexity of antibiotic resistance and improve the interpretation of ecological studies [20]. Continuing that idea, we have previously demonstrated that water in high-irradiated pristine environments was a source for isolating bacteria able to grow in the presence of antibiotics, and that the bacteria were also present in flamingos’ enteric biota, probably taken from the water where they feed [3]. In addition, we have found that several isolated bacteria present giant extra chromosomal linear elements, the so-called linear plasmids [21-23]. We found that the presence of linear plasmids might be related to the antibiotics-resistant dispersion. In this work, we attempt to study the total bacterial community under different selective pressures and the connection between the microbiota associated to lake water and flamingo feces.
We showed that the ability to grow in ATB or the rapid spread of this ability was abundant, diverse, and widely distributed in the water and feces of the studied high-altitude environments. As it was postulated by our group in previous publications [2, 3], UV radiation would be in connection with ATB resistances since under extreme UV stress, bacteria are known to increase mutational events, through a resistance mechanism named error-prone repair [24]. In many cases, spontaneous resistance to ATB is known to emerge under such mutagenic conditions, as consequence of mutagenesis modified potential target genes. In addition, a possible connection of oxidative stress resistances and an association with ATB resistances were also established [25]. As it was largely established that UV radiation produces high oxidative stress, thus a high-irradiated environment is expected to select oxidative stress-resistant bacteria, and this could also be in connection with ATB resistances found in more irradiated environments.
One the other hand, exposure of wild birds to human-generated wastewater presents a pathway for transfer of bacteria and the antibiotic resistance genes that they carry [26]. Water bodies of Pampean Lakes are threatened by many anthropic activities, resulting from land use, agriculture, and livestock, with the subsequent deposition of a significant amount of organic wastes, fertilizers, and pesticides [27-30]. Therefore, flamingos exposed to such sources could be colonized by microorganisms that are not typical of their natural habitats and are involved in the dissemination of multidrug-resistant bacteria since migration of flamingos, among lakes from Andean lakes in summer to Pampean lakes in winter, is an established phenomenon [31]. Our next challenge is subject to deeper studies the flamingo’s role as disseminators and/or reservoir of multidrug-resistant bacteria.
Mostly, band sequences identified in water samples were also found in feces. Thus we observed a connection between the bacterial community’s inhabitant flamingos intestinal and those of the water lake, where these birds obtain their food: community structure harboring similar ATB resistances were similar in both water and feces samples, sampled from the same lake. Special attention should be given to
A band corresponding to
As it was determined by our preview reports [2, 3], we confirm the idea that pathogenic organism resistant to multi-antibiotics are not a phenomena restricted to spoiled environments and that pristine environments could be considered as important reservoirs of bacteria like
HAAL – High Altitude Andean Lakes; ATBs – Antibiotics; DGGE – Denaturant Gradient Gel Electrophoresis
This work was supported by PIE CONICET 6268-6096, Fundación Antorchas Nº 14248-133, PICT-Agencia Nacional de Promoción Científica y Tecnológica Nº14498. María Verónica Fernández-Zenoff is recipient of a CONICET fellowship. Anna Neumann received financial support from DAAD.
An ionic liquid is a liquid salt consisting of anions and cations. Since Wilkes [1] synthesized a low melting point ionic liquid that is stable in air in 1992, there has been active fundamental research and engineering development directed at applications. In the field of tribology, where application is focused toward lubricants, the number of related papers [3]-[28] has increased every year since Liu et al. [2] published their research results in 2001. As a lubricant, ionic liquids are characterized by an extremely low vapor pressure, high thermal stability, and high ion conductivity. Based on these features, there are high expectations for the development of new ionic liquid applications as lubricants [29]-[37] in extreme environments, such as high temperatures [7]-[9] and vacuum [10]-[12], where the use of conventional lubricants is limited.
\n\t\t\tA lubricant must be used under various sliding conditions. Therefore, choosing an ionic liquid suitable for its application is necessary. Ionic liquids are also called designer’s liquids because various characteristics can be created by different combinations of anions and cations. Owing to this wide variety of choices, it is important to understand the characteristics of the ionic liquid targeted for use as a lubricant. However, at present details of the lubrication mechanism are still not clearly understood, so a trial-and-error approach is inevitable for selecting ionic liquids.
\n\t\t\tThis article introduces the advantages and issues related to the basic characteristics of ionic liquids as a lubricant, and it describes their future prospects, mainly for applications in vacuum.
\n\t\tIn general, the coefficient of friction is highest under dry friction conditions, where no lubricant is used. The use of a lubricant controls this type of friction conditions and may suppress damage to surfaces. Fig. 1 shows the Stribeck curve used in tribology. This figure shows the transition of the lubricating conditions of the sliding surfaces: the friction coefficient is the vertical axis, and the bearing characteristic number (fluid viscosity
Schematic of the stribeck curve; the friction coefficient as a function of the lubrication parameter: ηV/P. In this formula, η is the fluid viscosity, V is the relative speed of the surfaces, and P is the load on the interface per unit bearing width.
Because most ionic liquids are in liquid state near room temperature, they can be used as a base oil for the lubricant. In addition, their application as a grease [38] by mixing the lubricant with additives [4][5][16][22] and thickeners has also been examined. The required properties of the ionic liquid differ depending upon the lubricating state. Specifically, in boundary and mixed lubrication, a firm adsorption layer must be formed on the sliding surfaces to control adhesion in the real contact area. On the other hand, in hydrodynamic lubrication, the formation of a thick liquid film must cause load burden even in the region of high surface pressure and low speed; as a result, the viscosity characteristic becomes an important factor. However, because an excessive tribo-chemical reaction can increase wear and cause corrosion—thus increasing friction coefficient—the lubricating efficiency balance must always be considered.
\n\t\t\tTo decrease friction and control damage to the sliding surfaces, hydrodynamic lubrication without solid contact is desired. For hydrodynamic lubrication, viscosity bears an important role with regard to the lubricant quality. An ionic liquid is in liquid state at room temperature, and its viscosity largely depends on the combination of anions and cations; it can be as thick as malt syrup or as thin as water. The viscosity of liquids decreases when the temperature rises; ionic liquids are no exception. For lubricants, the relationship between the temperature and viscosity is expressed by the viscosity index (VI). In general, this index should show a small variation in viscosity. The VI of ionic liquid is higher than that of general minerals and synthetic oils (poly-α-olefin, PAO), as shown in Table 1. Fig. 2 shows the measured results for the temperature–viscosity relation of two ionic liquid mixtures made from the same cation ([BMIM][TFSI] and [BMIM][PF6]); this verified that different mixing ratios correspond to different viscosities [39]. This indicates the possibility of arbitrarily adjusting the viscosity by mixing several types of ionic liquids. Because of the advantages of low vapor pressure and high thermal stability, ionic liquids are especially suitable for hydrodynamic lubrication applications in special environments, such as high temperatures and vacuums. Applications in bearings under dynamic and static pressure are being examined [40].
\n\t\t\t\t\n\t\t\t\tFor lubricant and grease used in the elasto-hydrodynamic lubrication (EHL) state, such as for rotating bearings and gears, the dominant physical property influencing lubrication capability is the viscosity under high pressure, which can be up to several gigapascals. Ohno et al. [41][42] measured the high-pressure viscosity of a methylimidazole-type ionic liquid and reported the crystallization behavior of molecular characteristic crystals to be similar to liquid crystal under high pressure. Regarding the physical properties, such as the high-pressure viscosity index of ionic liquid, more data are expected to be reported in the future. However, behavior that causes hindrances in the EHL state, such as that reported by Ohno et al. [43], has not been reported.
\n\t\t\tViscosity properties of ionic liquids and base oils
*1: N-Methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide
*2: Trihexyl(tetradecyl)phosphonium bis(trifluoromethylsolfonyl)imide
*3: 1-Butyl-3-methylimidazolium tetrafluoroborate
*4: 1-Butyl-3-methylimidazolium hexafluorophosphate
*5: 1-Butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide
*6: 1-Butyl-3-methylimidazolium iodide
*7: 1-Ethyl-3-methylimidazolium dicyanamide
*8: 1-Butyl-3-methylimidazolium tricyanomethane
Viscosity property of mixed ionic liquids as a function of temperature
Most studies on the special tribological qualities of ionic liquids have been on the boundary lubricating capacity. The ionic liquids examined in these studies mainly use an imidazole derivative as the cation and fluorine as the halogen element, such as tetrafluoroborate [BF4], hexafluorophosphate [PF6], and bis(trifluoromethanesulphonyl)imide [TFSI], for the anion. Fig. 3 shows the results of an investigation into the lubrication capability of different ionic liquids. Bearing steel balls and disks were used as sliding materials. The conditions for friction evaluation were as follows: temperature = 50°C, load = 50 N, reciprocating frequency = 50 Hz, amplitude = 1 mm, and friction time = 60 min. Two types of ionic liquid ([BMIM][TCC] and [EMIM][DCN]) do not include halogen. On the other hand, ionic liquids containing halogen exhibit low friction and wear and show good boundary lubrication properties. When ionic liquid containing halogen is used for lubrication, metal fluoride forms on friction surfaces by a tribochemical reaction; because this reaction product operates as a boundary lubricating layer, satisfactory lubricity is shown.
\n\t\t\t\tLubricity of each ionic liquid for steel/steel sliding
On the other hand, ionic liquid containing a halogen such as fluorine has been known to cause corrosion in steel [16]-[22][44][45][46], aluminum alloy [17][21][22][45], bronze [45][46], and titanium alloy [9] sliding materials. The cause of corrosion has been reported to be the formation of hydrogen fluoride due to the decomposition of the ionic liquid; this is largely due to water being mixed into the ionic liquid as an impurity and participating in the reaction [21]. Decomposition and corrosion reactions of ionic liquid happen even in a static environment. However, it is more marked in a sliding environment. Because water from the surrounding atmosphere is mixed into the ionic liquid owing to enhancement by friction, metal fluoride formed on the friction surfaces is believed to further react with water by tribo-chemical reactions to generate hydrogen fluoride. Thus, corrosion occurs after friction. Fig. 4 shows the change in appearance of the friction surface for steel bearings after reciprocating sliding between the balls and disks, by using the hydrophobic ionic liquid [PP13][TFSI] as the lubricant in air at 50% relative humidity. Immediately after the rubbing test, no remarkable corrosion was seen. However, after exposure to air for 24 h, a color change was observed for all parts touched by the ionic liquid. SEM-EDX analysis verified the composition of the corrosion product, containing mainly fluorine and oxygen, in the surface marked with pit-shaped corrosion [47]. Even after the [PP13][TFSI] was applied to the bearing steel surface exposed to air for 1 week, the occurrence of corrosion could not be verified. Therefore, friction is thought to promote the corrosion reaction and the decomposition of ionic liquid.
\n\t\t\t\tof corrosion on disk specimen after sliding test with [PP13][TFSI] at 50°C in air:(a)0.1 h, (b)1.0 h, (c)8.0h,(d) 24 h
Although ionic liquids containing halogen have superior capacity in terms of boundary lubrication, they also have the problem of corrosion. There are three solutions to prevent corrosion.
\n\t\t\t\tBased on the discovery of the relation between corrosion and water contamination, if an ionic liquid is used in an environment where it is hard to mix water with a hydrophobic ionic liquid having a low impurity concentration, the corrosion reaction can be controlled. Fig. 5 shows the friction and wear characteristics of the halogen-containing hydrophobic ionic liquid [PP13][TFSI] in air and in dry nitrogen [47]. In a dry nitrogen atmosphere, the coefficient of friction was stable and low even at 200°C, and the wear in this atmosphere was less in comparison with that in air. In addition, further corrosion was not observed on the specimen rubbed in dry nitrogen and left in air after the rubbing test, as shown in Fig. 6. From this, it is possible to prevent the corrosion in environments such as a vacuum, where there are almost no occurrences of mixture with water.
\n\t\t\t\t\tComparison of friction and wear behavior of [PP13][TFSI] in air and in dry-nitrogen atmosphere
Optical micro-images of worn disk surfaces under lubrication with [PP13][TFSI] in air ((a),(b)) and dry-nitrogen ((c),(d)).(a) after 0.1 h, (b) after 24 h, (c) after 0.1 h and (d) after 24 h.
To control the occurrence of hydrogen halide, which causes corrosion, methods to form a protective film over the frictional surface to prevent excessive reaction between the halogen and metal from taking place have been considered. Fig. 3 compares the effect of the presence of phosphorus on friction and wear. [BMIM][PF6] and [BMIM][BF4] have the same cation but different anions; the former has phosphorus, whereas the latter does not. [PP13][TFSI] and [P(h3)3][TFSI] have the same anion but different cations: the former has phosphorus and the latter does not. Although the ionic liquids containing phosphorus have a somewhat higher coefficient of friction, they have substantially lower wear. Phosphorus in the ionic liquid is suspected to react with the frictional surface to form a phosphoric acid compound layer that is superior in wear resistance [19][23]-[25]; also, the formation of metal fluoride, which causes the occurrence of hydrogen fluoride, was controlled. For an ionic liquid containing phosphorus as a lubricant, because the advance of corrosion in a specimen left in air after rubbing was not observed, the suppression effect is believed to be a post-rubbing phenomenon.
\n\t\t\t\tTo completely remove the corrosion reaction that originates from halogen, halogen-free ionic liquids should be selected. However, as shown in Fig. 3, their boundary lubrication ability is generally inferior to that of halogen-containing ionic liquids. However, when comparing halogen-free ionic liquids [BMIM][TCC] and [BMIM][BCN], the difference in anion results in a difference in lubricity. The discovery of a halogen-free ionic liquid with good boundary lubrication ability that does not depend on the formation of a metal halide layer is possible [48].
\n\t\t\t\t\tFriction and wear properties of hard-coatings and sintered-ceramics under lubrication with [EMIM][DCN] and [BMIM][TCC].
\n\t\t\t\t\t\tFig. 7 shows the boundary lubricity of halogen-free ionic liquids corresponding to various wear resisting materials [49]. Although the lubrication ability of the two types of ionic liquid varied depending on the sliding materials, some samples showed good lubrication properties such as the combination of hydrogen-free diamond-like carbon (H-free DLC) and [BMIM][DCN]. Details on the lubricating mechanism of halogen-free ionic liquid are a future topic, but the application areas of halogen-free ionic liquid are expected to be broadened by selecting the combination of hydrogen-free diamond-like carbon with appropriate sliding materials.
\n\t\t\t\t\n\t\t\t\tIn a vacuum, especially for machines in outer space, a lubricant with low vapor pressure and temperature stability is required owing to exposure to a severe temperature environment [38][43][50]. At present, perfluoropolyether (PFPE) and multiple-alkylated cycropentane (MAC) or grease that designates these as the base oil are used as the liquid lubricants in outer space because of their low vapor pressure. The lubricity of these lubricants is known to be improved by adding extreme pressure agents and the like, but issues such as evaporation of the additive and a decrease in the permanent viscosity of the base oil [43] remain to be resolved. As a non-additive base oil, ionic liquid has been reported to be superior to PFPE and MAC in terms of lubricity. In addition, as a grease, ionic-liquid-type grease has superior boundary lubrication capacity in a vacuum compared to systems of PFPE and MAC [38][50]. Regarding research on radiation for utilization in space, ionic liquid has been verified to have radiation resistance [38].
\n\t\t\t\tOn the other hand, in industrial vacuum equipment, inevitable atmospheric release exists on sliding surfaces in most cases. Thus, extra attention must be paid to corrosion when using a halogen-containing ionic liquid. Furthermore, regarding rust prevention due to exposure to atmosphere, although the adsorption-type rust-preventive agent has been reported to be effective, these results were collected under static conditions, and the effect under sliding is unclear.
\n\t\t\tWith regard to out-gassing in a vacuum, the occurrence condition, gas type, and allowed quantity differ depending on the application of the vacuum. In the case of materials for outer space equipment, measurement of the outgas (ASTM E595-93) requires a vacuum below 7 × 10-3 Pa for the sample and collector plate, a sample temperature of 125°C, and a collector temperature of 25°C (kept for 24 h) to calculate the loss mass ratio (mass change before and after test) (TML, total mass loss) and reagglutination material ratio of the collector plate (CVCM, collected volatile condensable materials) [51]. Ionic liquid based greases were developed and verified that the TML and CVCM are below 1.0% and 0.1% respectively [38]; this satisfies NASA’s recommended values. In addition, the quantity of outgas that occurs during rubbing in an ionic liquid has been reported to be less than that in PFPE and MAC [50]. Thus, the outgas quality of an ionic liquid as a lubricant for space equipment applications can be concluded to be superior.
\n\t\t\t\tPartial pressure changes of generated gas species from ionic liquid during sliding under vacuum condition. (a) Titanium disk, (b) Steel disk
On the other hand, in some semiconductor processes, outgas is a contamination that can barely be tolerated. In such cases, attention must be paid to selecting the ionic liquid and sliding material. Fig. 8 shows the change in partial pressure in a vacuum during a sliding test between a SiC pin and a titanium or iron disk using N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA TFSI) as the lubricant [11]. When the iron was rubbed, a slight partial pressure rise at just m/e = 30 and 58 was verified. However, in the case of titanium, a clear rise in partial pressure was seen at m/e = 15, 30, 58, and 86 upon friction. Similar out-gassing results were seen in friction tests using aluminum. During the tribo-chemical reaction between the metal sliding surface and ionic liquid to form a metal fluoride, part of the ionic liquid decomposition is believed to release outgas into the vacuum. To suppress friction associated with out-gassing, a combination with a sliding surface having low chemical activity, such as DLC, is effective [52].
\n\t\t\tIonic liquids have various superior qualities that traditional lubricants do not have. The development of new lubricating systems that use these features is expected. However, there are still remaining issues that must be overcome for the wide application of ionic liquids, such as disintegration and corrosion problems related to the stability and durability of ionic liquids and guidelines on optimizing the combination with sliding materials. However, these are fundamental issues that belong to the understanding of fundamental mechanisms of tribology rather than problems specific to ionic liquids. Thus, an attempt has recently been made to use an ionic liquid as a model chemical compound for understanding the action mechanism of lubricant additives. By developing an understanding of this type of fundamental lubricating mechanism, progress toward the use of ionic liquid lubricants can be expected.
\n\t\tAs a company committed to the wider dissemination of knowledge, IntechOpen supports the OAI Metadata Harvesting Protocol (OAI-PMH Version 2.0).
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