\\n\\n
These books synthesize perspectives of renowned scientists from the world’s most prestigious institutions - from Fukushima Renewable Energy Institute in Japan to Stanford University in the United States, including Columbia University (US), University of Sidney (AU), University of Miami (USA), Cardiff University (UK), and many others.
\\n\\nThis collaboration embodied the true essence of Open Access by simplifying the approach to OA publishing for Academic editors and authors who contributed their research and allowed the new research to be made available free and open to anyone anywhere in the world.
\\n\\nTo celebrate the 50 books published, we have gathered them at one location - just one click away, so that you can easily browse the subjects of your interest, download the content directly, share it or read online.
\\n\\n\\n\\n\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'
IntechOpen and Knowledge Unlatched formed a partnership to support researchers working in engineering sciences by enabling an easier approach to publishing Open Access content. Using the Knowledge Unlatched crowdfunding model to raise the publishing costs through libraries around the world, Open Access Publishing Fee (OAPF) was not required from the authors.
\n\nInitially, the partnership supported engineering research, but it soon grew to include physical and life sciences, attracting more researchers to the advantages of Open Access publishing.
\n\n\n\nThese books synthesize perspectives of renowned scientists from the world’s most prestigious institutions - from Fukushima Renewable Energy Institute in Japan to Stanford University in the United States, including Columbia University (US), University of Sidney (AU), University of Miami (USA), Cardiff University (UK), and many others.
\n\nThis collaboration embodied the true essence of Open Access by simplifying the approach to OA publishing for Academic editors and authors who contributed their research and allowed the new research to be made available free and open to anyone anywhere in the world.
\n\nTo celebrate the 50 books published, we have gathered them at one location - just one click away, so that you can easily browse the subjects of your interest, download the content directly, share it or read online.
\n\n\n\n\n'}],latestNews:[{slug:"webinar-introduction-to-open-science-wednesday-18-may-1-pm-cest-20220518",title:"Webinar: Introduction to Open Science | Wednesday 18 May, 1 PM CEST"},{slug:"step-in-the-right-direction-intechopen-launches-a-portfolio-of-open-science-journals-20220414",title:"Step in the Right Direction: IntechOpen Launches a Portfolio of Open Science Journals"},{slug:"let-s-meet-at-london-book-fair-5-7-april-2022-olympia-london-20220321",title:"Let’s meet at London Book Fair, 5-7 April 2022, Olympia London"},{slug:"50-books-published-as-part-of-intechopen-and-knowledge-unlatched-ku-collaboration-20220316",title:"50 Books published as part of IntechOpen and Knowledge Unlatched (KU) Collaboration"},{slug:"intechopen-joins-the-united-nations-sustainable-development-goals-publishers-compact-20221702",title:"IntechOpen joins the United Nations Sustainable Development Goals Publishers Compact"},{slug:"intechopen-signs-exclusive-representation-agreement-with-lsr-libros-servicios-y-representaciones-s-a-de-c-v-20211123",title:"IntechOpen Signs Exclusive Representation Agreement with LSR Libros Servicios y Representaciones S.A. de C.V"},{slug:"intechopen-expands-partnership-with-research4life-20211110",title:"IntechOpen Expands Partnership with Research4Life"},{slug:"introducing-intechopen-book-series-a-new-publishing-format-for-oa-books-20210915",title:"Introducing IntechOpen Book Series - A New Publishing Format for OA Books"}]},book:{item:{type:"book",id:"23",leadTitle:null,fullTitle:"Modern Pacemakers - Present and Future",title:"Modern Pacemakers",subtitle:"Present and Future",reviewType:"peer-reviewed",abstract:"The book focuses upon clinical as well as engineering aspects of modern cardiac pacemakers. Modern pacemaker functions, implant techniques, various complications related to implant and complications during follow-up are covered. The issue of interaction between magnetic resonance imaging and pacemakers are well discussed. Chapters are also included discussing the role of pacemakers in congenital and acquired conduction disease. Apart from pacing for bradycardia, the role of pacemakers in cardiac resynchronization therapy has been an important aspect of management of advanced heart failure. The book provides an excellent overview of implantation techniques as well as benefits and limitations of cardiac resynchronization therapy. Pacemaker follow-up with remote monitoring is getting more and more acceptance in clinical practice; therefore, chapters related to various aspects of remote monitoring are also incorporated in the book. The current aspect of cardiac pacemaker physiology and role of cardiac ion channels, as well as the present and future of biopacemakers are included to glimpse into the future management of conductions system diseases. We have also included chapters regarding gut pacemakers as well as pacemaker mechanisms of neural networks.\nTherefore, the book covers the entire spectrum of modern pacemaker therapy including implant techniques, device related complications, interactions, limitations, and benefits (including the role of pacing role in heart failure), as well as future prospects of cardiac pacing.",isbn:null,printIsbn:"978-953-307-214-2",pdfIsbn:"978-953-51-6423-4",doi:"10.5772/556",price:159,priceEur:175,priceUsd:205,slug:"modern-pacemakers-present-and-future",numberOfPages:626,isOpenForSubmission:!1,isInWos:1,isInBkci:!1,hash:null,bookSignature:"Mithilesh Kumar Das",publishedDate:"February 14th 2011",coverURL:"https://cdn.intechopen.com/books/images_new/23.jpg",numberOfDownloads:362257,numberOfWosCitations:60,numberOfCrossrefCitations:28,numberOfCrossrefCitationsByBook:4,numberOfDimensionsCitations:95,numberOfDimensionsCitationsByBook:5,hasAltmetrics:1,numberOfTotalCitations:183,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"April 13th 2010",dateEndSecondStepPublish:"May 11th 2010",dateEndThirdStepPublish:"September 15th 2010",dateEndFourthStepPublish:"October 15th 2010",dateEndFifthStepPublish:"December 14th 2010",currentStepOfPublishingProcess:5,indexedIn:"1,2,3,4,5,6",editedByType:"Edited by",kuFlag:!1,featuredMarkup:null,editors:[{id:"61931",title:"Prof.",name:"Mithilesh",middleName:"Kuma",surname:"M Das",slug:"mithilesh-m-das",fullName:"Mithilesh M Das",profilePictureURL:"https://mts.intechopen.com/storage/users/61931/images/1618_n.jpg",biography:"Associate Professor of Clinical Medicine\nKrannert Institute of Cardiology, Indiana University School of Medicine 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3092",title:"Anopheles mosquitoes",subtitle:"New insights into malaria vectors",isOpenForSubmission:!1,hash:"c9e622485316d5e296288bf24d2b0d64",slug:"anopheles-mosquitoes-new-insights-into-malaria-vectors",bookSignature:"Sylvie Manguin",coverURL:"https://cdn.intechopen.com/books/images_new/3092.jpg",editedByType:"Edited by",editors:[{id:"50017",title:"Prof.",name:"Sylvie",surname:"Manguin",slug:"sylvie-manguin",fullName:"Sylvie Manguin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"72",title:"Ionic Liquids",subtitle:"Theory, Properties, New Approaches",isOpenForSubmission:!1,hash:"d94ffa3cfa10505e3b1d676d46fcd3f5",slug:"ionic-liquids-theory-properties-new-approaches",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/72.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"2270",title:"Fourier Transform",subtitle:"Materials Analysis",isOpenForSubmission:!1,hash:"5e094b066da527193e878e160b4772af",slug:"fourier-transform-materials-analysis",bookSignature:"Salih Mohammed Salih",coverURL:"https://cdn.intechopen.com/books/images_new/2270.jpg",editedByType:"Edited by",editors:[{id:"111691",title:"Dr.Ing.",name:"Salih",surname:"Salih",slug:"salih-salih",fullName:"Salih Salih"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"54585",title:"Properties of GaP Studied over 50 Years",doi:"10.5772/67852",slug:"properties-of-gap-studied-over-50-years",body:'\nDescribed herein are studies initiated by one of the authors (SLP) in 1961. Further studies on the same samples were conducted in the later 1960s through 1970s, then again in the 1980s, 1990s, and 2000s making these a very unique set of semi‐centennial observations [1–34, 40–42].
\nOne of the most important findings of this study was the observation, first recognized in the 1980s, of a significant improvement over time in the properties of GaP crystals under ambient temperature and pressure. In particular, it was found that ordering of host and impurity atoms improved over time as did the GaP mechanical properties, luminescence with tunable spectral characteristics, and nonlinear optical effects, not observable in the freshly prepared (imperfect) crystals.
\nOver time, as confirmed by 50 years of experiments on the same samples, driving forces, such as diffusion along concentration gradients, strain relaxation associated with clustering, and minimization of the free energy associated with properly directed chemical bonds between host atoms, results in an ordered redistribution of impurities and host atoms in the crystal. In the particular case of GaP, as well as other compounds possessing highly volatile components, attempt to accelerate these processes through annealing at increased temperatures cannot be successful due to the potential for thermal decomposition (in GaP—due to P desorption). Accordingly, successful thermal processing of these compounds can only take place at temperatures below the sublimation temperatures of their volatile constituents, requiring a longer annealing time. For instance, as evaluated in the framework of the Ising model, the characteristic time of the substitution reaction during N diffusion along P sites in GaP:N crystals at room temperature constitutes 15–20 years [2]. Hence, the observations of highly excited luminescence and some other phenomena in the crystals made in the 1960–1970s and in the 1980–1990s were then compared with the results obtained in 2005–2014 under similar experimental conditions.
\nThe long‐term ordering of doped GaP and other semiconductors has been observed as an important accompanying process, which only can be studied using the same unique set of samples and decade time scales. More specifically, the optical and mechanical properties of single crystalline GaP and some other semiconductors, also grown in the 1960s, have been analyzed. Comparison of the properties of the same crystals was performed in the 1960s, 1970s, 1980s, and 1990s [1, 3–17] along with those of newly made GaP nanocrystals [18–20] and freshly prepared bulk single crystals [21–24]. Jointly with Refs. [25, 26, 31–34], this review provides a generalization of the results on these long‐term observations of luminescence, absorption, Raman light scattering, and microhardness of the bulk single crystals in comparison with the same properties of the high‐quality GaP nanocrystals. It is shown that the combination of these characterization techniques elucidates the evolution of these crystals over the course of many decades. It also clarifies the ordered state brought about by prolonged room‐temperature thermal annealing, and the useful optical properties that accompany such ordering. It is demonstrated that long‐term natural stimuli that improve the perfection of crystals prevail over other processes and can lead to novel heterogeneous device systems and new semiconductor devices with high temporal stability.
\nIn this chapter, we summarize more than 50 years of results of the study of evolution of the properties of the GaP crystals stored under normal conditions and, on this basis, we propose a new approach to resource‐saving production of optoelectronic materials and unique devices based on them.
\nThe method to grow gallium phosphide crystals from GaP solution melt was chosen due to the significant temperature reduction of the process and the presence of large amounts of solvent which dramatically reduce impurities from the container. Note that lamellar crystals grown from this solution melt are the most convenient and economical material in the manufacture of many semiconductor devices.
\nThe influence of the following factors on the quality of the grown single crystals has been investigated: (1) quantity and chemical nature of impurities; (2) geometric shape of the container and conditions of heat rejection; (3) accuracy of the temperature control; and (4) cooling rate and the law of heat‐sink cooling.
\nThe solution‐melt method of GaP growth is described in detail in Refs. [1, 3, 7]. The focus here is only on the most essential details of the crystal growth.
\nSynthesis, alloying, and crystallization of Ga‐P mixture were combined in a single cycle. Influence of impurities on the growth of GaP crystals was investigated using the highest‐purity industrially produced materials at that time (1960) in the former USSR. The growth of the crystals was conducted in a sealed quartz container that was introduced into the programmable furnace with a vibrating mount to agitate the mixture of Ga, P, and any chosen dopant. This agitation was performed to facilitate chemical reaction between components and to avoid a possible explosion of the container in dangerous temperature points of the process of mass crystallization.
\nIn order to study the form and quality of growing crystals, the crystallization process could be interrupted at any temperature below the point of liquidus. This interruption was achieved with the help of a specially designed growth container and its programmable heating furnace, which allow to stop the change of temperature of the solution melt, to identify and examine grown to this time crystals (see details in Refs. [1, 3]).
\nThe solution, carefully heated to slightly over 400°C, was held at this temperature for about 2 h to transform the red phosphorus precursor into its white form. Then, the heating process may be smoothly prolonged until a temperature of about 1200°C is reached, which exceeds the liquidus point for 5% P solution in Ga (1123°C) and creates appropriate conditions for Ga‐P reactions. After about 1–3 h, the samples are gradually cooled at a rate of 30°C/h to 600–700°C and then the furnace is turned off and naturally cooled to room temperature.
\nThe following impurities were doped into the GaP individually: Cu, Zn, Cd, In, Si, Ge, Sn, S, Se, Te, Ni, Cr, Fe, Co, Sm, La, Gd, and Sm2O3. Typical features of the doped GaP crystals (size, color, polarity, lamellar structure, twinning, the dislocation structure, and others) were compared with similarly grown but undoped crystals.
\nIt was found [1, 3] that the properties of the crystals depend on the chemical nature as well as on the quantity of the selected impurities. Their small admixtures did not significantly change the form of the crystals, while significant change of the crystallization environment composition created changes in forms of growth. It was also found that the following factors most significantly influenced the morphology of GaP crystals grown from the Ga‐P solution: (a) the degree of supersaturation, which depends on the temperature of the solution and (b) its first derivative with time; the conditions of the heat crystallization removal and the accuracy of the temperature control in the solution.
\nChanging crystallization conditions, mainly the rate of cooling of the melt, significantly affects the morphology of crystals. Accordingly, the increase of the cooling rate thus reduced the size of the crystals, but the dislocation density was not changed and was primarily determined by the concentration and chemical nature of the impurities. The number of crystals having isometric forms increased with decreasing of cooling rate resulting in the simultaneous improvement of the quality of the crystal surface. Uneven removal of heat from the walls of the container led to the formation of up to 30‐mm crystal needles elongated in the direction of the heat removal.
\nSignificant impact on the crystal quality provides more accurate temperature control. The crystals obtained with the accuracy of temperature control ±0.5°C had the perfect planes (111), low dislocation density, and dimensions that were two to three times larger than the crystals obtained at the same conditions, but with the accuracy of ±5°C. Crystals reached 25 mm in length and had the dislocation density of ∼103 cm−2, which is significantly less than that of the crystals obtained with low accuracy of the temperature control [1, 3].
\nBased on the findings of this investigation, let us now present an overview of the growth of lamellar GaP crystals. The first crystals, having the form of dendritic needles with the length of the order of 5 mm and thickness of 0.15 mm, were grown at the temperature of 1107°C, which is approximately 16°C of undercooling. The crystals represent thin plates in the form of rhombs, triangles, or hexagons. The twinning on the transverse cross sections was observed at the study of microsections and cleaved facets. It turned out that the lamellar GaP crystals contain the plane of twinning, parallel to the planes (111) [1, 22].
\nThe growth process of lamellar crystals can be formally divided into two components: the tangential growth in the plane (111) and layer‐by‐layer growth in the direction normal to the plane (111). Because the ratio of Ga and P atoms differed significantly from the stoichiometry, it is assumed that diffusion is the process that determines the rate of growth. Accepting the two‐stage model of lamellar crystal growth, let us consider the ratio of the contributions of the tangential growth in the plane (111) and layer‐by‐layer growth in the direction normal to the plane (111). The growth in the tangential direction is limited by diffusion and by the size of the previous layer, that is, is determined by the initial conditions and the shape and size of the plates, formed during the cooling of the solution melt 10–20° below the point of liquidus. Since the formation of the initial crystals occurs in a very short time, the growth in the tangential direction is difficult to control, as it is in the case of the dendritic crystal growth. The growth in the direction normal to the plane (111) is sensitive to the fluctuations of the degree of supersaturation, resulting from the thermal motion of atoms and temperature fluctuations. In general, the better the homogeneity and perfection of the surface of the lamellar GaP crystals, the lesser the ratio of the time necessary for the formation of flat embryos on it, to the time for which the embryo is created on the next plane. The latter, obviously, in an extreme extent depends on fluctuations of the degree of supersaturation in different points of the growing plane and at different points in time. With the deterioration of precision temperature control, the number of fluctuations increases and low‐quality crystals grow in the conditions of “entanglement” of the above‐noted characteristic times. Small fluctuations of supersaturation also are probably the cause of twinning planes. Increase of the accuracy of temperature regulation promotes some reduction in the number of twins, and this fact also confirms the notable influence of fluctuations on the twinning [1, 3, 34].
\nThus, deteriorations of quality or shape of defects of GaP plates during their growth from Ga‐P melt solution were observed in the following cases: (1) at a considerable increase of concentration of impurities in the GaP solution and dependently on the chemical nature of the chosen impurity and (2) at the change of the crystallization conditions, namely, at the sufficient deterioration of the cooling velocity control or in the case of nonuniform heat removal from the container for the crystal growth.
\nProcesses for the formation of dendritic needles and their transformation to platelet crystals take place over a small temperature and time interval. As a result, they are hard to control, while crystal growth is easily controlled in the direction normal to the plate (111), due to the sensitive nature of velocity of the solution cooling and accuracy of the temperature control [1, 3].
\nThe above‐stated results imply that only high‐quality and carefully controlled growth equipment will yield the highest‐quality GaP crystals. However, despite these precautions, the subsequent text shows how to considerably increase the quality and utility of freshly prepared GaP crystals.
\nGaP nanoparticles have been prepared using white P under mild aqueous low‐temperature synthesis conditions using two colloidal methods from mixtures of GaCl3•nH2O and dry NaBH4 or Na3P and GaCl3 diluted in toluene. Details are provided in Refs. [17–20].
\nUniform GaP nanoparticles formed following ultrasonic and other treatments were found to exhibit improved quality in their colloidal stability and brightness of luminescence at room temperature, which is found to be broadband with a maximum at 3 eV. Also discussed is their use in GaP/polymers nanocomposites for light‐emissive device structures [28, 30, 31].
\nPhotoluminescence, spontaneous Raman scattering, and X‐ray diffraction, together with high‐resolution electron microscopy of the nanoparticles prepared under different conditions, were compared with those from bulk single crystals.
\nFor the first time to the best of our knowledge, it is shown that well‐aged GaP bulk crystals as well as high‐quality GaP nanoparticles have no essential difference in their luminescence behavior, brightness, or spectral position of emitted light.
\nWhile bulk and thin‐film GaP has been successfully commercialized for many years, their application in nanocomposites as a new optical medium has only recently received attention. This section reviews recent efforts to advance the quality of GaP nanoparticles for light‐emissive devices based on polymer/GaP nanocomposites.
\nThis activity is the important milestone in the creation of the nanocomposites for advanced light‐emissive device structures because GaP nanoparticles exhibit important luminescent and electroluminescent properties and are compatible with selected polymer matrices.
\nThe quality of GaP nanoparticles was improved using mild aqueous synthesis and different colloidal reactions of Ga and P sources in toluene [26–37]. Ultrasonication and ultracentrifugation were applied during the synthesis and selection of nanoparticles to increase their quality and to control the size of the nanoparticles.
\nIn 2005, the authors developed methods to fabricate GaP nanoparticles [18]. So, the technology and properties of the nanoparticles obtained in 2005–2006 and later [27–30] are a good reference point for comparison of the new data provided herein [31].
\nThe first samples of GaP nanoparticles having a distinct luminescence at room temperature were obtained by hydrothermal method from aqueous solutions at a relatively low temperature (120–200°C). It was found that the composition of the nanoparticles corresponds to stoichiometric GaP. The colloidal method provides a good opportunity to control the conditions of the synthesis, to decrease power inputs, and to increase the quality of nanoparticles concerning their purity and uniformity of their dimensions. In actuality, the single parameter, which may be controlled in the other methods, is temperature, while using colloidal methods one can control nucleation of nanoparticles as well as velocity of their growth. The other important advantage of the colloidal method is the ability of the so‐called “capping,” that is, to isolate nanoparticles from each other, to prevent their agglomeration during storage, simultaneously inhibiting their further growth. Therefore, we have elaborated the methods of GaP nanocrystals colloidal synthesis using NaBH4 and Na3P compounds.
\nPolyglycidyl methacrylate (PGMA), polyglycidyl methacrylate‐co‐polyoligoethyleneglycol methacrylate (PGMA‐co‐POEGMA), and biphenyl vinyl ether (BPVE) polymers were used to synthesize GaP nanocomposites suitable for light‐emissive luminescent device structures. Film nanocomposites of good quality with high brightness and broadband luminescence were realized. The thickness of the polymer composite film was within 250–300 nm defined from atomic force microscope (AFM) experiment. The following procedures have been used in the fabrication of the nanocomposites:
\nGaP powder was ultrasonicated in methylethylketone (MEK) using Branson 5210 ultrasonic bath. Then, PGMA was added to the MEK solution. GaP to polymer ratio was less than 1:10.
GaP powder was dispersed in water‐ethanol mixture (1:1 volume ratio) and ultrasonicated using Branson 5210 bath for 120 min. Then, PGMA‐co‐POEGMA was added in the form of water‐ethanol mixture (1:1 volume ratio) solution. GaP to polymer ratio was less than 1:3. Nanocomposite films were deposited on quartz slides via dip coating.
GaP powder was dispersed in the biphenyl vinyl ether/dichloromethane (BPVE/DCM) solution; the solution was stirred and filtered from the excess of the powder. A few milliliter drops of the settled solution were casted onto silicon wafer.
More details on the preparation and characterization of our GaP/polymers nanocomposites can be found in Refs. [31, 33–36].
\nFigure 1a shows transmission electron microscope (TEM) images of GaP nanoparticles obtained from aqueous synthesis. One can see GaP nanoparticles, having characteristic dimensions less than 10 nm. The washed, thoroughly ultrasonicated, and dried nanopowder contains mainly single nanoparticles, while the same powder obtained without ultrasonic treatment consists of the clusters with the dimensions of the order of 100 nm.
\nTEM image of GaP thoroughly ultrasonicated and dried nanoparticles obtained by mild aqueous synthesis (a) and AFM topography image of the GaP/PGMA nanocomposite (b) [
Figure 1b shows atomic force microscope (AFM) topographic images of the GaP/PGMA film nanocomposite deposited by dip coating from a suspension in water‐ethanol mixture solution on the surface of a silica substrate. The AFM images demonstrated that no significant aggregation was caused by the polymerization. In general, individual particles were observed. The relevant luminescence spectra are presented in Figures 2 and 3.
\nSpectra of luminescence from GaP/PGMA‐co‐POEGMA nanocomposites. Nanoparticles have been prepared using white P by mild aqueous synthesis and stored as the dry powder (spectrum 1) or suspension in a liquid (spectrum 2) [
Luminescence spectra of 2 GaP/BPVE nanocomposites produced on the base of two parties of GaP nanoparticles prepared using different conditions [
Figure 2 shows the spectra for GaP/PGMA‐co‐POEGMA nanocomposites. Comparing the results for the nanocomposites prepared from GaP powder or suspension (Figure 2, spectra 1 and 2, respectively), it was established that the best quality has the nanocomposites obtained from the nanoparticles stored as a suspension in a suitable liquid (see spectrum 2).
\nAccording to our measurements, the matrix polymers PGMA‐co‐POEGMA or BPVE used in this work provide no contribution to the luminescence spectra of luminescence based on these matrixes GaP nanocomposites presented in Figures 2 and 3, so, the nanocomposite spectra coincide with those obtained from the relevant GaP powders or suspensions. It is noted that in the GaP/BPVE nanocomposite, the position of the luminescent maximum can be changed between 2.5 and 3.2 eV and the brightness is 20–30 more than in the PGMA and PGMA‐co‐POEGMA matrixes. We explain the broadening of the luminescence band and the shift of its maximum to low‐photon energies in luminescence of the nanocomposite based on the GaP powder in Figure 2, spectrum 1, by the presence of the nanoparticles with the dimensions of 10–100 nm in the powder.
\nFigures 2 and 3 present a clear image of the quantum confinement effect in the GaP nanoparticles. In accord with our data, the shift is about a few tenths of eV and, obviously, it is impossible to explain only through this effect the dramatic 1 eV enhancement to the region of luminescence at 300°K on the high‐energy side of the spectrum.
\nIn order to explain this interesting phenomenon, we postulate that the nanocrystals, much like the ideal long‐term‐ordered bulk GaP single crystals, exhibit this increase in blue‐shifted luminescence due to (a) negligibly small influence of defects and non‐radiative recombination of electron‐hole pairs and very high efficiency of their radiative annihilation, (b) high perfection of nanocrystal lattice, and (c) high transparency of nanocrystals due to their small dimensions for the light emitted from high points of the GaP Brillouin zones, for instance, in the direct transitions Γ1c–Γ15v between the conductive and valence bands with the photon energy at 300°K equal to 2.8 eV [39] and (d) high efficiency of this so‐called “hot” luminescence. On the basis of these improved technologies for the preparation of GaP nanoparticles and GaP/polymer nanocomposites, we can control within broad limits the main parameters of luminescence and expect therefrom to create a framework for novel light‐emissive device structures using this dramatic 1‐eV expansion of GaP luminescence to the UV region.
\nThus, the film device structures, elaborated by us, demonstrate broadband luminescence in the region from UV until yellow‐red with controlled width and position of maximum with the luminous intensity up to 1 cd compared with industrial light‐emitting diodes.
\nInvestigating gallium phosphide (GaP) crystals grown by the author in the 1960s, clear improvement of their optical and mechanical properties was noted for the first time only after 10–12 years. It was unusual and interesting in the situation when all inorganic nature around us usually deteriorates in time. Therefore, the decision was taken to investigate, to understand, and to use this phenomenon in the future. In short, the investigation process can be described as follows.
\nFigure 4 provides a comparison of the evolution in luminescence spectra at low temperatures (80 K and below) from GaP:N over a period of 25 years. It is seen over this period zero‐phonon line A of single N‐impurity‐bound excitons and their phonon replica are narrower in their line widths when compared to the freshly prepared single crystals. Further, as expected, zero‐phonon line and replica in samples aged at room temperature for 25 years shift spectral position depending upon the concentration of N impurities (Figure 4b, spectra 1–3) according to Refs. [38, 39], while the same freshly prepared crystals exhibited broader luminescence line widths with increasing nitrogen content (Figure 4b, spectrum 4). These, along with other half‐centennial findings, including modifications in luminescence kinetics, spontaneous Raman scattering, X‐ray diffraction, absorption spectra, micro‐hardness, and density of dislocations, that are reported elsewhere [1, 3–24], strongly suggest that close‐to‐ideal GaP:N crystals form over time due to the equally spaced disposition of N impurities instead of their chaotic distribution in the same freshly prepared crystals.
\nEvolution of the GaP:N luminescence with time and nitrogen concentration at the temperature of 15 K. (a) Zero‐phonon line of the bound exciton A and its transversal acoustic (TA) and longitudinal optic (LO) phonon replica in as‐prepared (4) and 25‐year long‐term‐ordered (1) crystals. (b) Zero‐phonon line A as a function of nitrogen (N) concentration. 1–3: 25‐year‐old crystals. 4: as‐prepared. Curves 1 through 4 represent samples with nitrogen concentrations of 1017, 1018, 1019, and 1018 cm−3, respectively [
As first noted in Ref. [23], these results suggest a new type of crystal lattice in which the host atoms occupy their proper (equilibrium) positions in the crystal, while the N impurities are periodically substituted into the lattice portion into short chains of equal length. According to the data obtained from Raman light scattering [10, 14], host atoms of this new lattice develop harmonic vibrations, and high degree of lattice perfection leads to an abrupt decrease in the non‐radiative recombination and an increase of efficiency and spectral range of luminescence.
\nStimulated emission of light in these temporally ordered crystals (Figure 5b) also is observed. As was shown in Ref. [23], the GaP:N crystals aged for at least 40 years possess no discrete impurity level for N‐bound excitons in the forbidden gap. They also demonstrated a uniform luminescence from a broad excitonic band instead of the narrow zero‐phonon line and its phonon replica as observed from the less‐aged, 25‐year‐old crystals.
\nLuminescent spectra and schematic representation of the forbidden gaps (Δ
Thus, long‐term‐ordered GaP:N crystals demonstrate uniform bright luminescence from a broad excitonic band instead of the narrow zero‐phonon line and its phonon replica in disordered and partly ordered (25‐year‐old) crystals. This is due to the fact that ordered crystals have no discrete impurity level in the forbidden gap. To the best of our knowledge, such transformation of a discrete level within the forbidden gap into an excitonic band (Figure 5a, b) is observed for the first time. In this case, the impurity atoms regularly occupy the host lattice sites and affect the band structure of the crystals, which are now a dilute solid solution of GaP‐GaN with regular disposition of N atoms instead of freshly prepared GaP doped by occasionally located N atoms. Note that the increase of luminescence excitation in case of partly ordered GaP:N (Figure 5a, dotted line) leads to a broad luminescence band as a result of bound exciton interaction [9], while in the case of perfectly ordered crystals (Figure 5b), one can see an abrupt narrowing of the luminescence band due to stimulated emission in defect‐free crystals. Earlier, in freshly prepared crystals, we observed a clear stimulated emission from a GaP:N resonator at 80 K [5], as well as the so‐called superluminescence from GaP single crystals having natural faceting. Presently, our ordered crystals have a bright luminescence at room temperature that implies their perfection and very low light losses. In our studies [14, 23], we demonstrate that the stimulated emission in long‐term‐ordered GaP is also developed even at room temperature by electron‐hole recombination of an electron at the bottom of the conduction band with a hole at the top of the valence band and the LO phonon absorption.
\nIt is necessary to note that the very important for optoelectronics long‐term ordering and considerable improvement of the semiconductor crystal lattice and accompanying phenomena have been discovered and observed over decade time scales only due to grown in 1960th [1, 3, 7] unique collection of samples and control of evolution of their properties for 50years. And up to now, this collection of long‐term‐ordered perfect GaP single crystals gives opportunities to find deep fundamental analogies in properties of the perfect single crystals and nanoparticles as well as to predict and to realize in nanoparticles and perfect bulk crystals new interesting properties and applications. Jointly with Refs. [3, 7, 9–17, 21–27, 31–34], this section is a generalization of the results on long‐term observation of luminescence, absorption, and Raman light scattering in bulk semiconductors in comparison with some properties of the best to the moment GaP nanocrystals. Combination of these characterization techniques elucidates the evolution of these crystals over the course of many years, as well as the ordered state brought about by prolonged room‐temperature thermal annealing, and the interesting optical properties that accompany such ordering. We demonstrate that long‐term natural stimuli result in perfection of our crystals, which can lead to novel heterogeneous systems and new semiconductor devices with high temporal stability.
\nWe further improved upon the preparation of GaP nanocrystals using the known methods of hydrothermal and colloidal synthesis [29–31].
\nThe highest‐quality GaP nanoparticles have been prepared using hydrothermal or colloidal synthesis from white phosphorus at a decreased temperature (125°C) and intense ultrasonication. It has been established that the maximum shift to ultraviolet and the best quality, in general, are from nanocomposites obtained from the nanoparticles stored as a suspension in a suitable liquid.
\nAs noted earlier, different defects of high concentration in freshly prepared GaP single crystals completely suppress any luminescence at room temperature due to the negligible quantity of free path for non‐equilibrium electron‐hole pairs between the defects and their non‐radiative recombination, while the quantum theory predicts their free movement in the field of an ideal crystal lattice. It was also shown the long‐term‐ordered and therefore close‐to‐ideal crystals demonstrate bright luminescence and stimulated emission repeating behavior of the best nanoparticles with pronounced quantum confinement effects.
\nFigure 6 compares the luminescence spectra of our long‐term (up to 50 years)‐ordered GaP single crystals (spectrum 1) to that from high‐quality GaP nanoparticles and their GaP nanoparticles/polymers nanocomposites [15, 17]. Nanocrystals stored as dry powder demonstrate rather broad luminescent band with maximum at 2.8 eV (Figure 6, spectrum 2), while the nanocrystals of about 10‐nm sizes, thoroughly separated and distributed in a suspension, which prevents their coagulation, mechanical, and optical interaction, exhibit bright narrow‐band luminescence with maximum at 3.2 eV, approximately 1 eV above the position of the absorption edge in GaP at 300°K (Figure 6, spectrum 3).
\nLuminescence of perfect bulk GaP single crystals (1) in comparison with the luminescence of GaP nanoparticles and GaP/polymers nano‐composites (2, 3). Nanoparticles were prepared from white P by mild aqueous or colloidal synthesis at decreased temperature, stored as dry powder (spectrum 2) or suspension in a liquid (spectrum 3). Details can be found in Refs. [
The broadening of the luminescence band and the shift of its maximum to low‐photon energies in the nanocomposite is explained based on the different dimensions (between 10 and 100 nm) of the GaP powder. Meanwhile, the nanocomposites on the basis of the suspensions containing only approximately 10‐nm nanoparticles exhibit bright luminescence with maximum at 3.2 eV due to high transparency of 10‐nm nanoparticles for these high‐energy‐emitted photons and pronounced quantum confinement effect.
\nOur first attempts to prepare GaP nanoparticles [18, 27] yielded room‐temperature luminescence with maximum shifted only to 2.4 eV in comparison with the achieved now new maximum at 3.2 eV achieved today. It confirms significant progress in the technology of GaP nanoparticles and GaP/polymers nanocomposites. On the basis of these improved approaches to prepare GaP nanoparticles and GaP/polymer nanocomposites, we can change the main parameters of luminescence within the broad limits, and to create a framework for novel light‐emissive device structures using dramatic 1‐eV expansion of GaP luminescence to UV region.
\nThe role and application of bound excitons in nanoscience and technology are discussed in this section. Bound excitons are well studied in semiconductors, especially in gallium phosphide doped by nitrogen (GaP:N). Doping of GaP with N leads to isoelectronic substitution of the host P atoms by N in its crystal lattice and to the creation of the electron trap with a large capture cross section. Therefore, any non‐equilibrium electron in the vicinity of the trap will be captured by N atom, attracting a non‐equilibrium hole by Coulomb interaction and creating the bound exciton—short‐lived nanoparticle with the dimension of the order of 10 nm (it is the Bohr diameter of bound exciton in GaP:N). Note that none of the nanotechnology methods are used in the creation or selection of dimensions of these nanoparticles—only natural forces of electron‐hole interaction and electron capture by the traps are necessary for the creation of these nanoparticles. As a result, we get something like neutral short‐lived atom analog—a particle consisting of heavy negatively charged nucleus (N atom with captured electron) and a hole. The so‐called “zero vibrations” do not destroy possible solid phase of bound excitons having these heavy nuclei that give an opportunity to reach their crystal state—short‐lived excitonic crystal.
\nTaking into account the abovementioned results, a model for the crystal lattice and its behavior at a high level of optical excitation for well‐ordered N‐doped GaP (Figure 7) can be suggested. At the relevant concentrations of N, the anion sublattice can be represented as a row of anions where N substitutes P atoms with the period equal to the Bohr diameter of the bound exciton in GaP (approximately 10 nm) (Figure 7a). At some level of excitation, all the N sites will be filled by excitons, thereby creating an excitonic crystal (Figure 7b), which is a new phenomenon in solid‐state physics and a very interesting medium for application in optoelectronics and nonlinear optics [4, 15, 17, 25, 26, 32–34].
\nThe models of the well‐ordered GaP:N [
Thus, using bound excitons as short‐lived analogs of atoms and sticking to some specific rules, including the necessity to build the excitonic superlattice with the identity period equal to the bound exciton Bohr dimension in the GaP:N single crystal, we get a unique opportunity to create a new solid‐state media—consisting of short‐lived nanoparticles excitonic crystal, obviously, with very useful and interesting properties for application in optoelectronics, nanoscience, and technology.
\nThe ability of matter to emit light of definite wavelengths and intensity depends on many factors; among them are the details of its band structure and crystal quality. Applied to light‐emissive materials and device structures, the quality is characterized by the concentration of the defects damaging light emission due to non‐radiative electron‐hole recombination on these defects. The ways for minimization of expected losses of the light in non‐radiative electron‐hole recombination are (1) decrease of concentration of the defects in the material grown by an improved method; (2) considerable quality improvement of GaP crystal structure discovered by us during long‐term (tens of years) ordering of the host and impurity atoms, and (3) application of nanocrystals with the dimensions less than the free paths of electrons and holes in the chosen light‐emissive material.
\nProperties that can be used to achieve light emission at a definite spectral region include (1) selection of the material on the basis of its band structure peculiarities and the value of the forbidden gap, which as a rule sizes up the maximum value of the emitting photons; (2) doping of the selected material by impurities or, on the contrary, precise purification of the chosen material for the creation of new channels of light emission; and (3) selection of the temperature and/or excitation level that to change contribution of different channels into light emission due to their disappearance or saturation.
\nIt is impossible or, at least, very difficult to realize all the above‐noted possibilities in a single material. Therefore, the present technologies of light‐emissive optoelectronics employ diverse range materials using very complicated and expensive technologies for their fabrication with the necessary application parameters. Down‐selecting a set of various materials applied currently in optoelectronics at the maintenance or even improvement of their high parameters and quality is one of the most important goals for reduction in price and wide application in the practice of electronic devices. The most impressive demonstration of this approach would be the selection of a suitable material, the development of a peculiar technology of its preparation, its interesting properties and prospects for application in optoelectronics instead of a huge number of various materials and their technologies.
\nSophisticated growth technique, knowledge of crystal growth mechanisms, of different processes, improving or deteriorating in time the prepared crystals, and the relevant comprehensive experience are necessary for the preparation of the perfect, free or almost free of contamination and doped GaP single crystals.
\nHowever, in the manufacture of artificial crystals, we are faced with the need to fabricate them for a very short time compared with the times for which naturally perfect crystals are grown. For example, a hundred years passes before the growing in the nature crystal acquires the dimensions necessary for its use as feedstock in jewelry making, while the commercial growth of moderately perfect semiconductors takes only a few hours. In such a short time, its own atom or dopant diffusing through the crystal usually cannot absolutely exactly occupy the places intended for them in ideal crystal lattice. This gives rise to lattice defects, which, in turn, hinder the achievement of perfect devices. Manufactured on the basis of such materials, greatly reduce their lifetime, as well as make it impossible manifestation of some very interesting and useful for the application of the effects observed in advanced materials. Significant levels of funds are spent on searching and implementing methods for creating materials, not existing in the nature, that can, even if in a narrow field of application and at short time service, replace the material with a perfect crystal lattice and the necessary concentration and location of dopants. Hence, there is an urgent need to develop methods for the creation of an ideal semiconductor material the required parameters for use in electronics. In this case, it will disappear or substantially decrease the need to develop a plurality of individual costly technology to produce a plurality of different materials with a limited resource and service applications, and as a very important result for any country involved in the production and use of electronic materials—a giant savings and the possibility of redeployment to other needs of funds spent on the production of low‐quality materials and products.
\nUsing the long‐term‐ordered perfect GaP or similar on behavior and properties material in electronic industry instead of current elaboration of very expensive and labor‐consuming technologies for diverse materials with their limited application spectral region and other parameters, we get a big commercial, scientific, and technology advantage from their fabrication and application.
\nWe hope that the methods based on the application of this long‐term evolution of the important properties of our unique collection of semiconductor single crystals [31–34] as well as the combined methods of laser‐assisted and molecular beam epitaxies [40–42] elaborated by us promise a novel approach to the development of a new generation of optoelectronic devices.
\nThe epitaxial methods, elaborated by us [40–42], will be applied to the fabrication of device structures with artificial periodicity; together with classic methods of crystal growth, they can be employed to realize impurity ordering that would yield new types of nanostructures and enhanced optoelectronic device performance.
\nThe long‐term, tens of years ordered GaP, its artificial analogs, and nanoparticles have very interesting and properties for different application, which give an opportunity to apply them in optoelectronics with high economic effect instead of a lot of different compounds currently used in optoelectronics.
\nThus, our half‐of‐a‐century collection of results provides a new approach to the selection and preparation of perfect optoelectronics materials (please see references to this chapter) and a unique opportunity to realize a new form of solid‐state host—the excitonic crystal [32–34]. These results confirm expedience of the efforts directed to the formation in GaP of the N‐impurity superlattice having a lattice period equal to the bound exciton dimension. As noted in this chapter and the relevant references, high‐quality material for industrial electronics can be prepared by storing freshly grown crystals for years in a special storage. Only old crystals with the attained necessary properties will then be annually retrieved for device fabrication, while new portions of fresh crystals will be placed for long‐term ordering at room temperature, as is done with wines and fine liquors.
\nAll of the results presented here and included in summary reviews [25, 26, 32–34] may sufficiently change the approach to the selection of materials necessary for electronics, and to make cheaper and simpler technology for the preparation of the selected materials and device structures on which they are based. This study of long‐term convergence of bulk‐ and nanocrystal properties [15, 17] brings a novel perspective to improving the quality of semiconductor crystals. The author\'s unique collection of pure and doped crystals of semiconductors grown in the 1960s provides an opportunity to observe and understand the physics behind the long‐term evolution of properties in these key electronic materials.
\nThe authors are glad to note that the broad discussion and dissemination of their joint results stimulate further collaboration with reliable partners from the USA, Russia, Italy, Romania, France, and other countries.
\nProf. Sergei L. Pyshkin expresses his cordial gratitude to his teachers, world‐known scientists late Profs Nina A. Goryunova, Nobel Prize Laureate Alexander M. Prokhorov, and academicians Rem V. Khokhlov and Sergei I. Radautsan. He is also very grateful to the US Department of State, Institute of International Exchange, Washington, DC, the US Air Force Office for Scientific Research, the US Office of Naval Research Global, Civilian R&D Foundation, Arlington, VA, the US Science & Technology Center in Ukraine, to his colleagues and coauthors from Clemson University, SC, University of Central Florida, FL, Istituto di elettronica dello stato solido, CNR, Rome, Italy, Universita degli studi, Cagliari, Italy, Lomonosov Moscow State University, Joffe Physico‐Technical Institute and State Polytechnical University, St. Petersburg, Ac. Scie. Institute of General Physics, Moscow, Russia, Institute of Applied Physics and Academy of Sciences of Moldova for support and attention to this protracted (1961 to present time) research.
\nAl-Mg alloys are non-heat-treatable aluminum alloys, which means they save energy in comparison with heat-treatable aluminum alloys. The Al-Si-Mg alloy, which is a heat-treatable aluminum alloy, is commonly used in automobile manufacture. For example, 6061 is used for forging, 6022 is used for sheet forming, and A357 and Silafont-37™ are used for casting and die casting. When aluminum alloys are used for automobile manufacture, Fe impurities are incorporated into the alloy, which causes AlSiFe intermetallic compounds to solidify when Al-Si-Mg alloys are recycled, reducing the Si content in the Al-Si-Mg alloy as AlSiFe intermetallic compound was crystallized. In Al-Mg-Si alloys, Mg2Si precipitates during aging, causing the strength of the Al-Si-Mg alloy to increase. When the AlSiFe intermetallic compounds solidify, this can cause a shortage of Si for the Mg2Si, and the strength may not increase sufficiently [1, 2]. As a result, Fe impurities have a reduced effect on Al-Mg alloys in comparison with Al-Si-Mg alloys. This is the second advantage of Al-Mg alloys over Al-Si-Mg heat-treatable alloys. Much less work has been done to investigate the effect of Fe impurities on the mechanical properties of Al-Mg alloys than for of Al-Si-Mg alloys [1, 2, 3, 4, 5].
To be suitable for the recycling of aluminum alloys, the selected process must satisfy the following two requirements: saving energy and improving the deterioration of the mechanical properties of the recycled alloy. In this paper, die casting, cast-forging, and roll casting were selected as the processes using the recycled Al-Mg alloys. Die casting can be used to produce aluminum alloy parts in one process with rapid solidification. Cast-forging has the advantage of energy-saving by process saving and the deformation effect, as the casting structure becomes the deformation structure [5, 6]. Roll casting has the advantage of energy-saving by process saving and rapid solidification. The intermetallic composition including Fe impurities becomes fine as a result of the rapid solidification.
In the recycling of aluminum alloys used for automobiles, the Fe content of the aluminum alloy is estimated to increase by 0.2% after shredding [7]. In this study, Fe contents of 0.2%, 0.4%, 0.6% and 0.8% were added to Al-Mg alloys to model recycled Al-Mg alloys. The addition of 0.8% Fe is considered to represent an alloy that has been recycled four times.
The Mg contents of the Al-Mg alloys used in this study were 4.5%, 6%, 8%, and 10%. The Mg content of 4.5% is near that of the 514.0 and 5182 aluminum alloys, and the Mg content of 8% is near that of 518.0. The four Fe contents were added to these four Al-Mg alloys, and test pieces were fabricated with the three selected processes. The mechanical properties were investigated via a tensile test. A deep drawing test was conducted on the plates made from the strips cast by the rolling caster. The suitability of the different Al-Mg alloys for recycling was then evaluated based on the obtained results.
A 500 kN cold chamber die casting machine (Hishinuma Machinery HC 50F) with an injection power of 100 kN and a sleeve diameter of 45 mm was used in this study. The plunger speed was 1.6 m/s. The test piece used for the tensile test and the spiral die used for the fluidity test are shown in Figure 1.
Test piece for the spiral die for the fluidity test and the tensile test.
The effects of the Mg and Fe contents on the fluidity were investigated. The results of the fluidity test are shown in Figure 2. The fluidity of the Al-Mg alloy decreased with increasing Mg content until 6% Mg and then increased as the Mg content was increased beyond 6%. The fluidity was greatest at an Mg content of 10% and progressively decreased at contents of 4.5%, 8%, and 6%.
Fluidity of Al-Mg alloys plotted against Mg content at different added Fe contents.
The fluidity increased with increasing Fe content, as shown in Figure 2. The flow stress at the semisolid condition decreased with increasing Fe content because the primary crystal became smaller and exhibited the mushy condition as the Fe content was increased. It is known that Fe is added to aluminum alloys during die casting to prevent the sticking of the solidification layer to the die. The heat transfer between the solidification layer and the die decreases with increasing Fe content because the contact condition between the solidification layer and the die worsens. As a result, the solidification time decreases and the fluidity increases. The increase of the Fe content during recycling; thus, does not make the fluidity worse but better.
Figure 3 shows the results of the tensile test of the die-cast test pieces plotted against the Mg content. Both the tensile stress and the 0.2% proof stress gradually increased with increasing Mg content. The elongation was maximized at 6% Mg and remarkably decreased with further increases in the Mg content to 8% and 10% Mg. The elongation of the Al-6%Mg was 17.4%, which is excellent. The elongation of the Al-10%Mg was 4.7%, which is better than that of A383, a popular alloy for die casting in Japan. These Al-Mg alloys have 0.2% proof stresses and elongations that are better than those of A383. These results demonstrate that the Mg content should be selected based on the target user. If ductility is important, Al-6%Mg is better, whereas if strength is important, Al-8%Mg or Al-10%Mg is suitable.
Effect of the Mg content of the Al-Mg alloy on the result of the tensile test of the die-cast test piece.
The tensile stress, 0.2% proof stress, and elongation of different Al-Mg alloys are plotted against added Fe content in Figures 4–6, respectively. When Fe was added, the tensile stress of each Al-Mg alloy was the same as or better than that of the corresponding Al-Mg alloy without added Fe. In die casting using recycled Al-Mg alloys, it was clear that the tensile stress was not degraded by increasing Fe content.
Tensile stress of different die-cast Al-Mg alloys plotted against added Fe content.
The 0.2% proof stress of die-cast Al-Mg alloys plotted against added Fe content.
Elongation of die cast Al-Mg alloys plotted against Fe content.
The 0.2% proof stress of the Al-Mg alloys with different added Fe contents is shown in Figure 5. The results indicate that the 0.2% proof stress was not significantly affected by the addition of Fe. The 0.2% proof stress of the Al-8%Mg and Al-10%Mg increased with the addition of Fe.
The elongation of the Al-Mg alloys with different added Fe contents is shown in Figure 6. The amount of decrease in the elongation with increasing Fe content was dependent on the Mg content of the alloy. The elongation of the Al-4.5%Mg decreased substantially with the addition of 0.2% Fe but changed little with further increases in Fe content up to 0.8%. The elongation of the Al-4.5%Mg with 0.8%Fe was 10.2%. It was clear that the elongation of the Al-4.5%Mg was not greatly influenced by the Fe content for Fe contents above 0.2%. The reduction in the elongation from an Fe content of 0 to 0.2% was smaller at greater Mg contents. The elongation of the Al-6%Mg decreased almost linearly from 17.4–8% as the Fe content increased from 0.2% to 0.8%. At Fe contents of 0.2% and 0.4%, the elongation of the Al-6%Mg was greater than that of the Al-4.5%Mg. The elongations of the Al-8%Mg and the Al-10%Mg gradually decreased with increasing Fe content. The elongations of the Al-4.5%Mg, Al-6%Mg, and Al-8%Mg, each with 0.8%Fe, and the Al-10%Mg with 0.4%Fe were greater than the elongation of the A383, which is 3.5%. This means that die-cast Al-Mg alloys may be suitable for recycling when die-cast Al-Mg alloys are used for automobile parts.
In cast-forging, a preform is cast near the net shape, which is suitable for forging. Processing and energy can be saved by cast-forging. The hot forging of a gravity-cast ingot was conducted as a model of cast-forging [8, 9, 10]. The process of gravity casting and hot forging is shown in Figure 7. This process is similar to cast-forging.
Schematic of process from gravity casting to hot forging.
The cooling rate of the gravity-cast Al-4.5%Mg ingot was 30.6°C/s. A specimen was made for the tensile test and tested to investigate the mechanical properties of the ingot. A square bar was cut out from the as-cast ingot and heated at 500°C for 1 h. The forging was conducted at 50% reduction. The mechanical properties of the hot-forged rectangular bar were investigated by tensile testing. The dimensions of the test piece are shown in Figure 1a.
The tensile test results for the gravity-cast Al-Mg alloys are plotted against the Mg content in Figure 8. As the Mg content increased from 4.5–10%, the tensile stress gradually decreased from 231 to 185 MPa, and the 0.2% proof stress gradually increased from 106 to 138 MPa. The elongation decreased greatly from 18–10% when the Mg content increased from 4.5–6%, after which it linearly decreased with further increases to the Mg content, down to 3% at an Mg content of 10%. The Mg content had a greater effect on the elongation than on the tensile stress or the 0.2% proof stress.
Tensile test results for gravity-cast Al-Mg alloys.
The results of the tensile test of the hot-forged gravity-cast ingot are plotted against the Mg content in Figure 9. The tensile stress, 0.2% proof stress, and elongation of all Al-Mg alloys were increased by the hot forging. The tendencies of the tensile stress and elongation for the Mg content were also changed by the hot forging. The tensile stress increased with increasing Mg content. The increase (improvement) of the tensile stress became greater as the Mg content increased. At Mg contents of 4.5% and 10%, the tensile stress increased from 231 to 287 MPa and 185 to 270 MPa, respectively, which corresponds to respective increases of 56 and 185 MPa. When the Mg content was 8%, the elongation was maximized, and the elongation of the Al-10%Mg was the smallest among the alloys. The elongation of the hot-forged Al-8%Mg was 24%, and that of the Al-10%Mg was 17%. These results show that the hot-forged Al-Mg alloys have excellent strength and ductility.
Tensile test results for hot-forged gravity-cast Al-Mg alloys.
Optical microscope images of the gravity-cast and hot-forged Al-Mg alloys are shown in Figures 10 and 11, respectively. The gravity-cast Al-Mg alloys had a dendrite microstructure, as shown in Figure 10; this is a typical structure for this type of casting. In contrast, there was not a dendrite structure in the hot-forged Al-Mg alloys, as shown in Figure 11, and the microstructure changed to a deformation structure as a result of the hot-forging. The grain size decreased as the Mg content increased until 8% Mg. This may contribute to the excellent mechanical properties of the Al-8%Mg alloy.
Optical microscope images of gravity-cast Al-Mg alloys.
Optical microscope images of hot-forged Al-Mg alloys.
The tensile stress, 0.2% proof stress, and elongation of the different Al-Mg alloys are plotted against the added Fe content in Figures 12–14, respectively. The tensile stress was not influenced by the Fe content, as shown in Figure 12. The 0.2% proof stress of the Al-4.5%Mg was almost uniform, and that of other Al-Mg alloys increased gradually with increasing Fe content, as shown in Figure 13. The results are shown in Figures 12 and 13 indicate that increasing the Fe content does not have a negative influence on the tensile stress or the 0.2% proof stress.
Tensile stress of the hot-forged gravity-cast Al-Mg alloys plotted against Fe content.
The 0.2% proof stresses of the hot-forged gravity-cast Al-Mg alloys plotted against Fe content.
Elongation of the hot-forged gravity-cast Al-Mg alloys plotted against Fe content.
At Mg contents of 4.5%, 6%, and 10%, the elongation decreased with increasing Fe content, as shown in Figure 14. The elongations of the Al-8%Mg with 0.2% and 0.4%Fe were 27.6% and 24.6%, respectively, and the elongation of the Al-8%Mg without added Fe was 24.0%. When the Fe content was 0.2%, the elongation did not decrease but increased. It is thought that the addition of Fe makes the elongation worse; however, in this case, the elongation increased. This means that when Fe impurities are incorporated during recycling, the elongation increases in comparison with that of the virgin alloy, demonstrating that upgrade recycling occurs. The elongation of the Al-8%Mg with 0.4%Fe was 24.6%, which means the added 0.4% Fe did not influence the elongation. The elongations of the Al-8%Mg with 0.6% and 0.8%Fe were 17.4% and 15.6%, respectively. The elongation of the hot-forged Al-8%Mg was excellent when the added Fe content was 0.8% or less. The elongation of the Al-10%Mg with 0.8%Fe was 9.5%, and that of the other Al-Mg alloys were greater than 9.5%. The hot-forged Al-Mg alloys have good elongation when Fe impurities are incorporated during recycling, with Al-8%Mg being particularly suitable for cast-forging and recycling.
It is known that centerline segregation occurs between the solidification layers in Al-Mg alloy strips cast using a twin-roll caster (TRC). It is difficult to reproduce the occurrence of this type of centerline segregation in strips cast using twin-roll casters. In this study, a single-roll caster equipped with a scraper (SRCS) was used to cast Al-Mg alloys strips without centerline segregation [11].
In the SRCS, the molten metal is solidified on the side of the one roll, and a centerline does not form. The free solidified surface is scribed into a flat surface by the scraper. The scraper load was 0.2 N/mm, and no crack was formed on either surface of the strip because of the small scraper load. A copper roll was used to increase the cooling speed and roll speed. In the conventional TRC, steel rolls are used. The thermal conductivity of copper is much larger than that of steel, and the cooling ability of a copper roll is thus greater than that of a steel roll. The casting speed of the SRCS was 30 m/min, whereas the casting speed of a conventional TRC is usually slower than 2 m/min. The excellent cooling ability of the copper roll enabled high-speed roll casting. Schematic illustrations of the SRCS and the area near the scraper are shown in Figure 15. Cross-sections of Al-4.5%Mg strips cast using the high-speed TRC and the SRCS are shown in Figure 16 [11, 12]. Centerline segregation occurred in the strip cast using the high-speed TRC and not in the strip cast using the SRCS.
Schematic illustrations of (a) a top-down view of a single-roll caster equipped with a scraper and (b) a view near the scraper.
Cross-sections of Al-4.5%Mg alloys cast using (a) a high-speed twin-roll caster and (b) a single-roll caster equipped with a scraper. The casting speed was 30 m/min.
Strips of Al-Mg alloys with Mg contents ranging from 4.5–10% could be continuously cast using the SRCS. The strip thickness is plotted against the Mg content in Figure 17. The strip became thicker as the Mg content increased. Two potential causes were considered to explain the relationship between the Mg content and the strip thickness. One is that the latent heat of the magnesium is smaller than that of the aluminum; thus, the latent heat of Al-Mg alloy decreases as the Mg content increases, which may then cause the strip thickness to increase with the Mg content. The other is that the amount of scribed and piled aluminum alloy under the scraper becomes greater as the Mg content increases, and the piled aluminum alloy becomes a part of the strip [12]. Therefore, the strip becomes thicker as the Mg content increases.
Strip thickness plotted against Mg content.
The surfaces of the Al-Mg alloy strips are shown in Figure 18. The scribed surface did not have a metallic luster, whereas the roll contact surface did. The Mg content did not influence the surface condition.
Surfaces of as-cast Al-Mg alloy strips.
The mechanical properties of the roll-cast Al-Mg alloy strips were tested by the tensile test. The cast strip was cold-rolled down to 1 mm and annealed at 360°C for 90 min. The dimensions of the test piece for the tensile test are shown in Figure 19.
Size of a test piece for the tensile test.
The results of the tensile test are shown in Figure 20. The tensile stress increased monotonically at a gradual rate with increasing Mg content. The 0.2% proof stress was almost constant at different Mg contents. The elongation increased with increasing Mg content up to 8% Mg and then substantially decreased at 10% Mg. Comprehensively, judging from the tensile test, the Al-8%Mg showed the best mechanical properties.
Tensile test results for roll-cast Al-Mg alloys with different Mg contents.
A deep drawing test was then conducted to investigate the ability of sheet forming. The cast strip was cold-rolled down to 1 mm and annealed at 360°C for 90 min. The diameter of the punch used for the deep drawing test was 32 mm. The deep drawing test was conducted under two conditions: with the roll-contact side of the strip facing outward and with the scribed surface facing outward. The results of the deep drawing test are shown in Figure 21. The limiting drawing ratio (LDR, the maximum ratio of circular blanks to the diameter of the die) of Al-4.5%Mg was 2.0 regardless of which side of the strip was facing outward. The LDR decreased with increasing Mg content. When the Mg content was 4.5% or 6%, the LDR was not affected by which side faced outward; in contrast, when the Mg content was 8% or 10%, the LDR was better when the roll-contact side faced outward. The difference between the LDRs in these two cases is not suitable for sheet forming. The Al-4.5%Mg was most suitable for sheet forming. The optimal Mg content for deep drawing was different from that obtained from the elongation in the tensile test. These results demonstrate that 514.0 aluminum alloy is suitable for sheet forming, and 518.0 aluminum alloy is suitable for the easy shape plate, which needs strength and elongation. This shows that the choice of Mg content depends on the purpose. The forming ability is the most important property for sheets used in automobile manufacture, and thus the Al-4.5%Mg is suitable for this purpose. The Al-4.5%Mg was used to make the model alloy of recycled Al-Mg alloys.
Limiting drawing ratio at different Mg contents.
Impurities of 0.2%, 0.4%, 0.6%, and 0.8% Fe were added to the Al-4.5%Mg to model the recycled Al-Mg alloy. The Al-4.5%Mg with Fe could be cast into a strip, as the addition of the Fe did not affect the ability of the roll casting; however, the addition of the Fe makes the strip hard and brittle. Edge cracks with lengths of 3 mm or less occurred in the Al-4.5%Mg with 0.8%Fe, and the cold rolling could be conducted on the strip down to 1 mm without breaking. When the added Fe content was less than 0.6%, edge cracking did not occur. The surfaces of the as-cast and the cold-rolled strips of the Al-4.5%Mg and the Al-4.5%Mg with 0.8%Fe are shown in Figure 22. There was no difference between the scribed and roll-contact surfaces of the cold-rolled virgin Al-4.5%Mg and Al-4.5%Mg with 0.8%Fe strips. It is thought that the increase in the Fe content does not affect the surface properties of the Al-4.5%Mg sheet cast by the SRCS after cold rolling.
Surfaces of as-cast and cold rolled strips of Al-4.5%Mg and Al-4.5%Mg with 8%Fe.
Cross-sections of the virgin Al-4.5%Mg and Al-4.5%Mg with 0.8%Fe strips are shown in Figure 23. The grain of the as-cast Al-4.5%Mg strip was almost uniform in the thickness direction. In the as-cast strip of Al-4.5%Mg with 0.8%Fe, the grain of the roll-contact side of the strip was finer than that of the scribed side. The effect of cooling speed on the grain size of the Al-4.5%Mg with 0.8%Fe was more apparent than in the Al-4.5%Mg. This is the influence of the added Fe. The Fe formed a crystal nucleus, and many crystals were made. As a result, the grain number increased and the grain size became small near the roll-contact side. The structure became a fine deformation structure after cold rolling and annealing.
Cross-sections of as-cast strip and cold rolled and annealed strip of Al-4.5%Mg and Al-4.5%Mg with 0.8%Fe. Annealing: 360°C for 90 min.
The results of the tensile test of the Al-4.5%Mg with Fe are shown in Figure 24. The tensile stress was almost uniform for the added Fe content. The 0.2% proof stress gradually increased with increasing Mg content, and the elongation very gradually decreased. The elongations of the Al-4.5%Mg and Al-4.5%Mg with 0.8%Fe were 30.3% and 28.6%, respectively. The reduction of the elongation with the addition of Fe was very small. The intermetallic compound including Fe may be very fine because of the rapid solidification of the rolling caster, and it did not make the elongation worse.
Result of tensile test of Al-4.5%Mg with Fe.
The LDR of Al-4.5%Mg with Fe is shown in Figure 25. The LDR did not decrease from 2.0 until the addition of 0.4% Fe. When the Fe content was 0.6%, the LDR was 1.9. The LDR when the scribed surface faced outward was the same as that when the roll contact surface faced outward until the Fe content was 0.6%. Therefore, the ultimate addition of Fe to the Al-4.5%Mg was 0.4%.
Limiting drawing ratio of Al-4.5%Mg with different Fe Contents.
The fluidity of the Al-Mg alloy decreased with increasing Mg content until 6% Mg and then increased as the Mg content was increased beyond 6%. The fluidity was greatest at an Mg content of 10% and progressively decreased at contents of 4.5%, 8%, and 6%. The fluidity increased with increasing Fe content.
The tensile strength and the 0.2% proof stress increased with increasing Mg content. The elongation of the Al-6%Mg was greater than that of the Al-4.5%Mg. The addition of Fe did not degrade the tensile stress and the 0.2% proof stress. The elongation was reduced by the addition of Fe. The elongations of the Al-4.5%Mg with 0.8%Fe and Al-6%Mg with 0.8%Fe were 10% and 8%, respectively. These elongations were as good as those obtained during die casting. The amount of decrease in the elongation of the Al-4.5%Mg was smaller than that of the Al-6%Mg. The Al-4.5%Mg is suitable for recycling when the recycled alloy was die-cast.
The mechanical properties of the gravity-cast Al-Mg alloys were increased by hot-forging. The tensile strength and the 0.2% proof stress increased as the Mg content increased. The elongation of Al-8%Mg was greater than that of the other Al-Mg alloys considered in this study. The addition of Fe did not degrade the tensile stress or the 0.2% proof stress. The elongation of all alloys except for the Al-8%Mg was degraded by the addition of the Fe. The elongation of the Al-8%Mg with 0.2%Fe was greater than that of the Al-8%Mg, and that of the Al-8%Mg with 0.4%Fe was the same as that of the Al-8%Mg. The elongation of the Al-8%Mg with 0.8%Fe was 15.6%, which is sufficiently large for a forged aluminum alloy. Al-8%Mg is thus suitable for cast-forging.
As the Mg content was increased, the tensile stress gradually increased, whereas the 0.2% proof stress remained almost constant. The elongation of the Al-8%Mg was greater than those of the other Al-Mg alloys. The LDR decreased as the Mg content increased. Therefore, the Al-4.5%Mg was selected as the most suitable for sheet forming among the roll-cast Al-Mg alloys. The tensile stress of the Al-4.5%Mg was almost uniform for the added Fe content. The 0.2% proof stress gradually increased with increasing Mg content, and the elongation very gradually decreased. The elongations of the Al-4.5%Mg and Al-4.5%Mg with 0.8%Fe were 30.3% and 28.6%, respectively. The LDR was 2.0 until an Fe content of 0.4%, and then it decreased with increasing Fe content for Fe contents greater than 0.6%. This shows that twice-recycled Al-4.5%Mg (Al-4.5%Mg with 0.4%Fe) cast using the roll-caster can be used for sheet forming.
This work was supported by SUZUKI FOUNDATION.
Authors are listed below with their open access chapters linked via author name:
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