<?xml version="1.0" encoding="ISO-8859-1"?><article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">
<front>
<journal-meta>
<journal-id>0870-8312</journal-id>
<journal-title><![CDATA[Ciência & Tecnologia dos Materiais]]></journal-title>
<abbrev-journal-title><![CDATA[C.Tecn. Mat.]]></abbrev-journal-title>
<issn>0870-8312</issn>
<publisher>
<publisher-name><![CDATA[Sociedade Portuguesa de Materiais]]></publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id>S0870-83122010000100005</article-id>
<title-group>
<article-title xml:lang="en"><![CDATA[Cold Spray Deposition of Titanium onto Aluminium Alloys]]></article-title>
</title-group>
<contrib-group>
<contrib contrib-type="author">
<name>
<surname><![CDATA[Barbosa]]></surname>
<given-names><![CDATA[M.]]></given-names>
</name>
<xref ref-type="aff" rid="A01"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname><![CDATA[Cinca]]></surname>
<given-names><![CDATA[N.]]></given-names>
</name>
<xref ref-type="aff" rid="A02"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname><![CDATA[Dosta]]></surname>
<given-names><![CDATA[S.]]></given-names>
</name>
<xref ref-type="aff" rid="A02"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname><![CDATA[Guillemany]]></surname>
<given-names><![CDATA[J. M.]]></given-names>
</name>
<xref ref-type="aff" rid="A02"/>
</contrib>
</contrib-group>
<aff id="A01">
<institution><![CDATA[,University of Porto Faculty of Engineering Departament of Metallurgical and Materials Engineering]]></institution>
<addr-line><![CDATA[Porto ]]></addr-line>
<country>Portugal</country>
</aff>
<aff id="A02">
<institution><![CDATA[,Universitat de Barcelona Departament de Ciència dels Materials i Enginyeria Metallúrgica CPT - Thermal Spray Centre]]></institution>
<addr-line><![CDATA[Barcelona ]]></addr-line>
<country>Spain</country>
</aff>
<pub-date pub-type="pub">
<day>00</day>
<month>06</month>
<year>2010</year>
</pub-date>
<pub-date pub-type="epub">
<day>00</day>
<month>06</month>
<year>2010</year>
</pub-date>
<volume>22</volume>
<numero>1-2</numero>
<fpage>48</fpage>
<lpage>56</lpage>
<copyright-statement/>
<copyright-year/>
<self-uri xlink:href="http://scielo.pt/scielo.php?script=sci_arttext&amp;pid=S0870-83122010000100005&amp;lng=en&amp;nrm=iso"></self-uri><self-uri xlink:href="http://scielo.pt/scielo.php?script=sci_abstract&amp;pid=S0870-83122010000100005&amp;lng=en&amp;nrm=iso"></self-uri><self-uri xlink:href="http://scielo.pt/scielo.php?script=sci_pdf&amp;pid=S0870-83122010000100005&amp;lng=en&amp;nrm=iso"></self-uri><abstract abstract-type="short" xml:lang="en"><p><![CDATA[The aluminium alloy 7075-T6 is widely used in aeronautic engineering due to its high mechanical resistance to weight ratio. Depending upon the environmental conditions, many types of corrosion mechanisms have been found to occur in aircraft structural aluminium alloys. A possible solution to improve the alloy’s behaviour is the deposition of a pure Titanium coating. At present the deposition of Titanium is limited to processes such as Electroplating, Chemical Vapour Deposition and Vacuum Plasma Spray. These traditional approaches are generally slow and expensive, while the common thermal spray processes have two major limitations which are the presence of porosity and oxides in the spray-deposited material. Since Titanium is a metal very sensitive to oxidation, it is proposed in the present work to deposit it onto Aluminium substrates by a novel thermal spray process known as “Cold Spray”. In this work, the influence of the gas pressure and temperature, and the powder feeding rate on the cold spray process and in the final coating characteristics was studied, and a dense pure titanium coating onto aluminium 7075 substrates, with thickness higher than 300µm and no microstructural changes was easily and fast obtained. It was possible to conclude that after optimization, the cold spray process when compared to the conventional thermal spray techniques, results in coatings with very good properties and cost-time effective (higher coating thickness can be achieved in less time and with less money investment), making it ideal for industrial applications.]]></p></abstract>
<abstract abstract-type="short" xml:lang="pt"><p><![CDATA[A liga de alumínio 7075-T6 é amplamente utilizada na aeronáutica devido à sua elevada relação resistência mecânica/peso. Porém está sujeita a diversas formas de corrosão resultantes dos diferentes ambientes em que se encontra inserida. Uma possível solução para melhorar o comportamento desta liga em situações de corrosão é o seu revestimento com uma camada de titânio puro. Porém, uma vez que o titânio é um metal extremamente sensível à oxidação, a sua deposição no estado puro encontra-se limitada a processos como a Electrodeposição, Chemical Vapour Deposition ou Vacuum Plasma Spray, que são técnicas lentas e dispendiosas. Este trabalho propõe a deposição deste metal num substrato de alumínio 7075 através de uma tecnologia inovadora de deposição a frio conhecida como Cold Spray. A influência de diferentes parâmetros de deposição é estudada (temperatura e pressão do gás de processo, velocidade de alimentação do pó) e foi possível obter um revestimento de titânio puro superior a 300µm, de forma rápida e fácil, sem quaisquer alterações microestruturais. Após optimização dos parâmetros de deposição, o processo de Cold Spray, quando comparado às técnicas de projecção térmica convencional, permite obter revestimentos com boas propriedades mecânicas de forma rápida e económica, tornando-o ideal para aplicações industriais.]]></p></abstract>
<kwd-group>
<kwd lng="en"><![CDATA[Aluminium]]></kwd>
<kwd lng="en"><![CDATA[Titanium]]></kwd>
<kwd lng="en"><![CDATA[Cold Spray]]></kwd>
<kwd lng="en"><![CDATA[Factorial Analysis]]></kwd>
<kwd lng="pt"><![CDATA[Alumínio]]></kwd>
<kwd lng="pt"><![CDATA[Titânio]]></kwd>
<kwd lng="pt"><![CDATA[Cold Spray]]></kwd>
<kwd lng="pt"><![CDATA[Análise Factorial]]></kwd>
</kwd-group>
</article-meta>
</front><body><![CDATA[ <p>DIA MUNDIAL DOS MATERIAIS 2009</p>      <p>2ª Menção Honrosa  ORDEM DOS ENGENHEIROS</p>      <p>&nbsp;</p>      <p><b>Cold Spray Deposition of Titanium onto Aluminium Alloys</b></p>      <p>&nbsp;</p>      <p><b>M. Barbosa<sup>(1) <a name="top0"></a><a href="#0">*</a></sup>, N. Cinca<sup>(2)</sup>,    S. Dosta<sup>(2)</sup>, J. M. Guillemany<sup>(2)</sup></b></p>      <p>(1)&nbsp;&nbsp; Departament of Metallurgical and Materials Engineering, Faculty    of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto,    Portugal; </p>      <p>(2)&nbsp;&nbsp;  Thermal Spray Centre (CPT). Dpt. Ciència dels Materials i    Enginyeria Metallúrgica. Universitat de Barcelona Martí i Franques 1, E-08028,    Barcelona, Spain.</p>      <p>&nbsp;</p>      <p><b>ABSTRACT</b></p>     ]]></body>
<body><![CDATA[<p>The aluminium alloy 7075-T6 is widely used in aeronautic engineering due to    its high mechanical resistance to weight ratio. Depending upon the environmental    conditions, many types of corrosion mechanisms have been found to occur in aircraft    structural aluminium alloys. A possible solution to improve the alloy’s behaviour    is the deposition of a pure Titanium coating. At present the deposition of Titanium    is limited to processes such as Electroplating, Chemical Vapour Deposition and    Vacuum Plasma Spray. These traditional approaches are generally slow and expensive,    while the common thermal spray processes have two major limitations which are    the presence of porosity and oxides in the spray-deposited material. Since Titanium    is a metal very sensitive to oxidation, it is proposed in the present work to    deposit it onto Aluminium substrates by a novel thermal spray process known    as “Cold Spray”. In this work, the influence of the gas pressure and temperature,    and the powder feeding rate on the cold spray process and in the final coating    characteristics was studied, and a dense pure titanium coating onto aluminium    7075 substrates, with thickness higher than 300µm and no microstructural changes    was easily and fast obtained. It was possible to conclude that after optimization,    the cold spray process when compared to the conventional thermal spray techniques,    results in coatings with very good properties and cost-time effective (higher    coating thickness can be achieved in less time and with less money investment),    making it ideal for industrial applications.</p>      <p><b>Keywords</b>: Aluminium, Titanium, Cold Spray, Factorial Analysis.</p>      <p>&nbsp;</p>      <p><b>RESUMO</b></p>     <p> A liga de alumínio 7075-T6 é amplamente utilizada na aeronáutica devido à    sua elevada relação resistência mecânica/peso. Porém está sujeita a diversas    formas de corrosão resultantes dos diferentes ambientes em que se encontra inserida.    Uma possível solução para melhorar o comportamento desta liga em situações de    corrosão é o seu revestimento com uma camada de titânio puro. Porém, uma vez    que o titânio é um metal extremamente sensível à oxidação, a sua deposição no    estado puro encontra-se limitada a processos como a Electrodeposição, Chemical    Vapour Deposition ou Vacuum Plasma Spray, que são técnicas lentas e dispendiosas.    Este trabalho propõe a deposição deste metal num substrato de alumínio 7075    através de uma tecnologia inovadora de deposição a frio conhecida como Cold    Spray. A influência de diferentes parâmetros de deposição é estudada (temperatura    e pressão do gás de processo, velocidade de alimentação do pó) e foi possível    obter um revestimento de titânio puro superior a 300µm, de forma rápida e fácil,    sem quaisquer alterações microestruturais. Após optimização dos parâmetros de    deposição, o processo de Cold Spray, quando comparado às técnicas de projecção    térmica convencional, permite obter revestimentos com boas propriedades mecânicas    de forma rápida e económica, tornando-o ideal para aplicações industriais.</p>      <p><b>Palavras chave: </b>Alumínio, Titânio, Cold Spray, Análise Factorial.</p>      <p>&nbsp;</p>      <p><b>1. Introduction</b></p>      <p>The aluminium alloy 7075-T6 is widely used in aeronautic engineering due to    its high mechanical resistance to weight ratio. Depending upon the environmental    conditions, many types of corrosion mechanisms have been found to occur in aircraft    structural aluminium alloys. A possible solution to improve the alloy’s behaviour    is the deposition of a pure Titanium coating; apart from the amelioration of    its performance against aggressive environments, titanium also offers many other    advantages such as weight savings, replacement costs and life cycle cost benefits.    At present the deposition of Titanium is limited to processes such as Electroplating,    Chemical Vapour Deposition and Vacuum Plasma Spray (VPS). These traditional    approaches are generally slow and expensive, while the common thermal spray    processes have two major limitations which are the presence of porosity and    oxides in the spray-deposited material. Within the thermal spray area, VPS has    been the only technique used, up to now, for titanium deposition, usually in    biomedical applications. Such process has, however, one main limitation which    is the high investment costs: expensive vacuum pumps and chambers of considerable    dimensions are required to generate and maintain the low-pressure environment    required for plasma treatment of workpieces [<a name="top1"></a><a href="#1">1</a>].    A promising alternative regarding its lower cost-effectivity and able to avoid    titanium reaction with oxygen is the use of the Cold Gas Spray technology.</p>      <p>Cold Spray is the name of the process in which powder particles, ranging from    5 to 100µm, are accelerated by injection into a high-velocity stream of gas    and then impinged upon suitable substrates. The expansion of a pressurized,    pre-heated gas through a converging-diverging nozzle is the reason why the powder    particles can impact the substrate with a velocity ranging between 300 and 1200    m/s, deforming and, consequently, bonding to it. The successive particles impacts    result in a uniform coating with very little porosity and high bond strength.    The term “cold spray” has been used due to the relatively low temperatures of    the expanded gas stream that exits the nozzle, and consequently the temperature    of the particulate material remains below its melting point and therefore the    resultant coating is formed in the solid state.     </p>      ]]></body>
<body><![CDATA[<p>Cold Spray offers many advantages but there are still some limitations inherent    to the process itself. Being a rather recent technology, no large-scale commercial    applications have yet established themselves in the broader thermal-spray marketplace.    The state-of-the-art is rapidly changing and, within the last years few authors    have reported their investigations dealing either with the influence of some    of the spraying parameters on the deposition efficiency or the understanding    of the bonding process [<a name="top2"></a><a href="#2">2</a>, <a name="top3"></a><a href="#3">3</a>,    <a name="top4"></a><a href="#4">4</a>, <a name="top5"></a><a href="#5">5</a>].    While in conventional Thermal Spraying processes, mechanical bonding is more    likely to occur when particles melt and rapidly solidify, at the moment, the    most accepted theory for Cold Spraying is the assumption of the existence of    the so-called “adiabatic shear instabilities”, which means that, at high particle    velocities, there is a thermal softening locally dominant over strain and strain-rate    hardening, which promotes an intimate contact between incoming particles and    substrate. This theory holds at high temperature and pressure. It also explains    the transition from erosion to cold spray adhesion, the behaviour of powder    deposition efficiency and the existence of an incubation time [<a name="top6"></a><a href="#6">6</a>].</p>      <p>Much fewer are addressed to properties evaluation such as corrosion [<a name="top7"></a><a href="#7">7</a>]    or mechanical performance [<a name="top8"></a><a href="#8">8</a>]. As far as    corrosion resistance is concerned, Wang et al., proved that the denser the coating    is, the lower is the corrosion current [<a href="#7">7</a>], whereas regarding    mechanical properties, Price et al., for example, in the attempt to evaluate    the fatigue resistance of Ti-CGS deposits for biomedical purposes, found that    those made the fatigue limit of Ti6Al4V substrates decrease, probably attributed    to the occurrence of induced tensile residual stresses [<a href="#8">8</a>].    Therefore, it is a challenging issue and there is still a long way to go.</p>      <p>The present paper is intended to optimize the cold spray process in order to obtain a fully dense titanium coating into a 7075-T6 aluminium alloy. The influence of spraying conditions by modification of temperature and gas pressure, as well as feeding rates and particle distribution, has been assessed. </p>      <p>&nbsp;</p>      <p><b>Cold Spray </b></p>      <p>Cold spray as a coating technology was initially developed in the mid-1980s,    by Anatolii Papyrin et al while studying models subjected to a supersonic two-phase    flow (gas + solid particles) in a wind tunnel [<a name="top9"></a><a href="#9">9</a>].    These Russian scientists successfully deposited a wide range of pure metals,    metallic alloys, polymers and composites onto a variety of substrate materials.</p>      <p>There is a very basic difference between the conventional techniques and the cold spray process. While in the first ones the device requires both thermal and kinetic energy for the coating formation, in cold spray only kinetic energy is used, although in many aspects, a generic cold spray gun (Fig. 1) looks very similar to some of the traditional thermal spray devices described earlier.</p>      <p>&nbsp;</p>         <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f1.jpg" width="464" height="156"></p>     
<p><b>Fig. 1</b> - Schematic diagram of a cold spray gun [<a href="#6">6</a>].</p>      ]]></body>
<body><![CDATA[<p>&nbsp;</p>     <p>Pressurized gas (generally air, nitrogen or helium) is heated, usually with    electrical energy, to temperatures generally in the range of 300-800°C and then    passed to a converging-diverging nozzle to create a supersonic gas jet. However,    unlike conventional thermal spray processes, the reason to heat the process    gas is not to melt the spray material. The gas is heated to increase its velocity    to supersonic values, while passing the converging-diverging nozzle [<a href="#6">6</a>,    <a name="top10"></a><a href="#9">9-15</a>]. The supersonic velocity is reached    due to the change of the Mach number (M=v/vs, where v is the gas velocity and    vs the sound velocity) along the nozzle. Since the gas expansion is followed    by a temperature decrease, which can in some cases even be below room temperature,    the process got the name of “Cold Spray”. Figure 2 shows a comparison of approximate    process temperature and particle velocity ranges for cold spray and conventional    thermal spray processes [<a href="#9">9</a>]. Analysing the image, it is clear    that cold spray occupies a unique position, offering exceptional low process    temperatures combined with high particle velocities.</p>     <p>&nbsp;</p>     <p><a name="f2"></a></p>     <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f2.jpg" width="355" height="244"></p>      
<p><b><a href="#topf2">Fig. 2</a></b> - Comparison of approximate process temperature    and particle velocity ranges for several common thermal spray processes and    cold spray [<a href="#9">9</a>].</p>         <p>&nbsp;</p>      <p>The process uses powder feedstock, in the range of 5-50µm in diameter, that    is then injected in the central axis of the cold spray gun. Since the powder    particles are only exposed to the hot process gas for a short period of time,    they arrive at the workpiece surface in the solid state, usually far below their    melting point. The particles are accelerated to velocities of the order of 500—1200m/s    before they impact the surface. If that velocity is sufficient for a given particle/substrate    pair, the solid particles plastically deform and flow upon impact, creating    an hydrodynamic flow instability at the interface between the incoming particle    and the underlying material, which results in bonding at the interface [<a href="#9">9-15</a>].</p>      <p>Because of its low-temperature operation, the cold spray process generally    offers a number of advantages over the thermal-spray material deposition technologies,    such as oxy-fuel, detonation gun, plasma, arc sprays, and others. Among these    advantages, the most important appear to be: (a) the amount of heat delivered    to the coated part is relatively small so that microstructural changes in the    substrate material are minimal or nonexistent; (b) due to the absence of in-flight    oxidation and other chemical reactions, thermally and oxygen-sensitive depositing    materials (e.g. copper or titanium) can be cold sprayed without significant    material degradation; (c) nanophase, intermetallic and amorphous materials,    which are not amenable to conventional thermal spray processes (due to a major    degradation of the depositing material), can be cold sprayed; (d) formation    of the embrittling phases is generally avoided; (e) macro- and micro-segregations    of the alloying elements during solidification which accompany the conventional    thermalspray techniques and can considerably compromise materials properties    do not occur during cold spraying. Consequently, attractive properties of the    powder material are retained in cold-sprayed bulk materials; (f) ‘‘peening’’    effect of the impinging solid particles can give rise to potentially beneficial    compressive residual stresses in cold-spray deposited materials in contrast    to the highly detrimental tensile residual stresses induced by solidification    shrinkage accompanying the conventional thermal-spray processes; and (g) cold    spray of the materials like copper, solder and polymeric coatings offers exciting    new possibilities for cost-effective and environmentally friendly alternatives    to the technologies such as electroplating, soldering and painting [<a name="top15"></a><a href="#7">7-15</a>].</p>      <p>&nbsp;</p>      ]]></body>
<body><![CDATA[<p><b>2. Experimental procedure</b></p>      <p>As said before, the main goal of this project is to optimize the cold spray    process in order to obtain a fully dense titanium coating into a 7075-T6 aluminium    alloy. To lead to optimization, the first step is to determine which factors    and which interactions between them are important in affecting the response.    For that, different process parameters will be varied and then the pair with    the highest deposition efficiency will be chosen. Finally, analysing the obtained    results, we will try to better understand the mechanisms leading to the bonding    formation between the coating and the substrate.</p>      <p>The powder used as feedstock was a microcrystalline Commercial Purity (CP)    titanium Grade 1 powder, from GfE (Metalle und Materialien GmbH), obtained by    ball milling. The powder particles are very angular and have a very irregular    form (Figure 3), which is consistent with the powder’s fabrication method and,    according to some authors, it represents an advantage for the cold spray process    since the irregular particles reach higher velocities and have a beneficial    contact behaviour by increasing particle/particle interaction during impact    [<a name="top14"></a><a href="#14">14</a>, <a name="top16"></a><a href="#16">16</a>].    Its particle size distribution shows Gaussian shape within the range of 22-90    microns. Such powder was sprayed onto 7075-T6 aluminium alloy coupons previously    degreased and scratched in order to promote better bonding by disrupting the    thin oxide layers in the surface and provide intimate contact particle-substrate.  </p>      <p>&nbsp;</p>     <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f3.jpg" width="379" height="307"></p>          
<p><b>Fig. 3</b> - Micrograph of powder morphology</p>      <p>&nbsp;</p>         <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f4.jpg" width="447" height="272">&nbsp;</p>      
<p><b>Fig.  4</b> - Cube representing the experimental domain. At the vertices,    are represented the chosen experiments.</p>      <p>&nbsp;&nbsp;</p>         ]]></body>
<body><![CDATA[<p>The cold spray equipment is a KINETICS®4000 (Cold Gas Technology, Ampfing,    Germany), with a maximum operating pressure of 40bar, temperature of 800°C and    limited to the use nitrogen as the propellant gas. In addition, KINETICS® 4000    is equipped with a pre-chamber of 120 mm in length connected to the gun nozzle    where powders are heated up by the hot gas for a longer time. Regarding the    spraying conditions, some parameters such as standoff distance, gun speed and    deposition angle were kept constant at 40 mm, 500 mm/s and 90º respectively,    based on previous experience. </p>      <p>In order to study the effect of pressure, temperature and feed rate, the most    convenient methodology was considered to be the realization of a factorial design.    This approach ensures the widest information with the lowest number of experiments;    when considering an experiment with n variables to be tested, each at two different    levels, a total of 2<sup>n</sup> experiments is required by the factorial design    to test every combination. The aim is to assess direct effects of the individual    variables and all their possible interactions on a physical quantity. Concerning    the present work n=3, this is 2<sup>3</sup> experiments. The importance of these    parameters in the cold spray process was evaluated by measuring the coating    thickness, porosity and hardness. In <a name="topf2"></a><a href="#f2">figure    2</a> a schematic representation of the experiment design can be found and table    1 is a matrix of the experiments. Table 2 shows how to quantify the influence    of the parameters interactions in the final result.</p>      <p>&nbsp;</p>      <p><b>Table 1</b> - Design of experiments: matrix of spraying conditions&nbsp;:    *(-)=[500-650]ºC, (+)=[650-800]ºC; **(-) =[25-32]  bar, (+)=[32-40]  bar, ***(-)=[1-3]rpm,    (+)=[4-6]rpm.</p>     <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05t1.jpg" width="347" height="198"></p>        
<p>&nbsp;    </p>        <p><b>Table 2</b> - Design of experiments: matrix of interactions.</p>          <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05t2.jpg" width="449" height="198"></p>      
<p>&nbsp;</p>     <p>The examination of the mounted and polished cross sections was performed in    a Scanning Electron Microscope (JEOL 5510 microscope) operated at 20 kV and    equipped with an Energy Dispersive Spectroscopy (EDS) for microanalysis. The    coating microstructure was revealed by etching with Keller´s reagent. The average    coating thickness was measured using the SemAfore Scanning Electron Microscope    software tool, while porosity was quantified by means of image analysis through    the Max Inspector Programme. Finally, microhardness was evaluated by means of    a Matsuzawa MTX-a Vickers equipment according to the ASTM E384-99 standard.    The mean values result from at least 20 indentations performed in the polished    cross-sections of the coatings. </p>      ]]></body>
<body><![CDATA[<p>&nbsp;</p>      <p><b>3</b>. <b>Results and discussion</b></p>      <p><b>3.1 Coatings Characterization</b></p>      <p>The coatings obtained with the different combinations of deposition parameters    presented before with numbers 1 to 8, are shown in Figure 5 with the respective    numeration.</p>     <p>&nbsp;</p>     <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f5.jpg" width="453" height="837"></p>     
<p><b>Fig. 5</b> - SEM micrographs of the titanium coatings obtained with the    parameters set from 1 to 8 respectively.</p>     <p>&nbsp;</p>     <p>The coatings were characterized according to their thickness (Figure 6), porosity    (Figure 7) and hardness (Figure 8).Observing  Figure 5, it is possible to distinguish    two different zones. In the top region from the surface to the boundary, there    are a lot of large pores. On the other hand, in the inner region from the boundary    to the substrate the coating has a dense microstructure. It is also possible    to observe that the size of the pores decreases with the increase of the depth    from the surface towards the boundary. This is due to the “peening” effect of    incoming high-velocity particles which tends to close the small pores and gaps    in the underlying material [<a href="#9">9</a>, <a name="top13"></a><a href="#13">13</a>,    <a name="top17"></a><a href="#17">17</a>]. </p>     <p>&nbsp;</p>     ]]></body>
<body><![CDATA[<p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f6.jpg" width="450" height="248"></p>     
<p><b>Fig. 6</b> - Graphic that illustrates the coating thickness obtained for    each set of parameters<b>.</b></p>     <p>&nbsp;</p>     <p><b><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f7.jpg" width="473" height="260"></b></p>     
<p><b>Fig. 7</b> - Graphic that illustrates the coating porosity obtained for    each set of parameters<b>.</b></p>     <p>&nbsp;</p>     <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f8.jpg" width="474" height="260"></p>     
<p><b>Fig. 8</b> - Graphic that illustrates the coating hardness obtained for    each set of parameters.</p>     <p>&nbsp;</p>     <p>From the analysis of Figure 5  and Figure 6, it can be observed that the coating thickness increases with the rising of the powder feeding rate. This was expected since almost the double amount of powder is used in the process. It also increases with the gas temperature for a feeding rate of 1-3rpm because a higher number of particles can reach the critical velocity and consequently bond to the substrate increasing the coating thickness. The same happens when pressure rises. On the other hand, for a feeding rate of 4-6rpm this is not verified maybe due to the accentuated rebound effect cause by the higher amount of particles (nearly the double) impacting the surface, which may interfere with the trajectory of incoming particles preventing them from impacting the substrate, or loose velocity, and consequently not bond, reducing the final coating thickness. The same is verified for a higher pressure.</p>      ]]></body>
<body><![CDATA[<p>The porosity level (Figure 7) was measured through the Max Inspector Programme.    It is important to notice that not all the voids present in Figure 5, 1 to 8,    are pores. Due to the high particle size distribution, in the same coating are    present particles with a size of 20&#956;m and particles with size of 100&#956;m,    which have a different behaviour during the flight and impact the substrate    at different velocities. This results that some particles, which didn’t have    enough energy to bond to their neighbours and should only cause erosion, get    trapped by the arriving particles and incorporate the coating. And when preparing    the sample for microstructural analysis, during the polishing operation, these    particles get detached leaving a void. This problem may origin results different    from the real ones. According to the images, the porosity decreases with the    rise of temperature, as expected, since the particles plasticity increases resulting    in a denser coating. However, the pressure influences negatively the porosity    level since it increases it. The porosity at 25-32bar varies from 2 to 4%, while    at 32-40bar it varies from 2 to 7%. It can then be considered that in the highest    interval, the particle velocity is so high that the rebound effect increases    the porosity (either due to the incoming particle not bonding or due to detaching    a poorly attached particle and so the erosion domain is reached). It is though    important to refer that this porosity is all concentrated in the top region    of the coating, and if this region was later mechanically removed, the coating    would be virtually 100% dense<sup>[<a name="topa0"></a><a href="#a0">a</a>]</sup>.    In the case of different feeding rates the obtained results are not comparable    since, at higher feeding rate, the coating thickness is much higher decreasing    the ratio (porosity area)/(coating area) which is how the programme calculates    the porosity.</p>      <p>The hardness was virtually the same for all the coatings (high error range) so the results for the influence of each parameter are not analysed (Fig. 8). It is worth to say that the wide particle size distribution may justify the wide hardness range, since when the indentation is preformed in the centre of a smaller particle the value is higher than in the centre of a bigger particle. Also the particle displacement due to being merely trapped instead of bonded represents an obstacle to a good analysis. </p>      <p>The influence of the parameters on the coating properties can be confirmed    by the factorial analysis represented in Table 3. </p>     <p>&nbsp;</p>     <p><b>Table 3</b> - Quantification of the parameters effect on the coating thickness,    porosity and hardness.</p>     <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05t3.jpg" width="855" height="161"></p>     
<p>&nbsp;</p>      <p>Regarding the coating thickness, the parameter with highest effect is the feeding rate since increasing it from 1-3 to 4-6rpm increases it in average 241&#956;m, followed by the temperature which increases it 27&#956;m and finally the pressure, which its increase decreases it 74&#956;m. This values are in accordance in the results expected at the beginning of this experiment, since a pressure increase should result in a denser coating and consequently in a smaller thickness.</p>      <p>The rise of temperature increases the coating thickness for a feeding rate of 1-3rpm, while it decreases it for a feeding rate of 4-6rpm. The interaction of the temperature and the feeding rate is then of big importance. When both the temperature and feeding rate are increased, at a fixed pressure, the coating thickness decreases 108&#956;m. This supports the statement that at high feeding rate and high temperature, the rebound effect overcomes the increase of plasticity and, instead of contributing to the growing of the coating, it causes erosion. The same reasoning can be made for the interaction of the other parameters.</p>        <p>For the porosity, according to the      obtained images and, consequently, the factorial analysis, it is once again      shown that it increases with the pressure for the previous explained reason.      And, as expected, it decreases with the temperature. For the feeding rate      the result may be deceiving as said before. The decrease in the porosity by      the interaction of the temperature and pressure is due to increase of the      particle plasticity overcoming the velocity increase. Finally, the hardness      was virtually the same for all the coatings (high error range) so its results      should not be considered.</p>      ]]></body>
<body><![CDATA[<p>Analysing the coatings structure and their properties it is possible to exclude    the coatings number 1, 3, 4, 5, 7 and 8 due to the high amount of pores and    to the very irregular surface.  It is then possible to state that the best combinations    of parameters are number 2 and 6 and their main difference is in the coating    thickness. Coating number 2 presents a thickness in the order of 400&#956;m    and coating number 6 in the order of 600&#956;m. Comparing these values to the    ones obtained by conventional thermal spray techniques, which are in the order    of 200&#956;m for higher number of gun passages, it is possible to say that    the optimum condition is number 2, since its thickness is more than sufficient    to form a protective coating for the required application, and the 600&#956;m    of coating 6 become too high making it less economically viable. However, the    high thickness that cold spray easily achieves suggests this process as a potential    alternative to laser cladding with the advantage of avoiding the heat affected    area.</p>      <p>&nbsp;</p>      <p><b>3.2 Further analysis of the selected coating</b></p>      <p>In order to verify the aluminium/titanium bonding strength and the hardness    profile of the area surrounding the interface, a nanoidentation test was preformed    in a Nano Indenter® XP system (Systems Corporation). The 75 nanoidentations    (matrix of 5x15) were conducted at constant load of 15mN and the results can    be seen in Figure 9. The zero value represents the interface zone, and the negative    distance corresponds to the substrate while the positive corresponds to the    titanium coating.</p>     <p>&nbsp;</p>     <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f9.jpg" width="474" height="230"></p>     
<p><b>Fig. 9</b> - Nanoidentation profile obtained for the sample number 2<b>.</b></p>     <p>&nbsp;</p>      <p>The hardness of the aluminium is in agreement with the standard values although it can be seen a slight increase with the approximation to the interface due to the hardening effect introduced by the constant bombing of particles. In the area right next to the interface this value drops due to a small thermal softening of the aluminium, which has low melting temperature, resulting from the high release of energy during the shock of the first particles. The hardness value at the interface is not high enough to allow saying that the bonding is very strong, but it is also not to low since it is in the same order as the aluminium, revealing that the bonding will be good. The hardness for the titanium coating is, as seen before, much higher than the bulk value due to the tamping effect. The hardness decreases with the distance to the interface since the amount of particles impacting on the already bonded ones also decreases, weakening the peening effect.</p>         <p>Also, XRD tests were performed to confirm that there was no reaction between    the titanium and the nitrogen/oxygen that confirmed that the obtained coating    is of pure titanium.</p>      ]]></body>
<body><![CDATA[<p>In order to better understand the bonding process, the TEM analysis of the    interface area was also conducted. In Figure 10,  A shows the Selected Area    Electron Diffraction (SAED) pattern corresponding to interface area represented    in B, where one can see the titanium zones, filled by dislocations, mixed with    the aluminium areas with their characteristic precipitates. The elemental analysis    of different regions indicated a composition gradient of the two elements which    indicates that solid-state diffusion as indeed occurred. The presence of an    amorphous zone that could indicate a localized fusion, as reported by Xiong    et al [<a name="top18"></a><a href="#18">18</a>], was not found, which doesn’t    mean that is not present since it is in the order of a few nanometres. Further    investigation should be conducted.</p>         <p>&nbsp;</p>     <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f10.jpg" width="474" height="241"></p>      
<p><b>Fig. 10</b> - A) SAED pattern and B) TEM micrograph of the interface aluminium/titanium    coating.</p>      <p>&nbsp;</p>      <p><b>3.3 Optimization</b></p>      <p>This wide size distribution that results in particles badly bonded between    them, and sometimes merely trapped, is the main reason to the high number of    voids and the non-uniformity (both hardness and morphology) of the coating.    In order to further optimize the process, a powder with a narrower size distribution    should be used. So, to analyse the importance of the particle size in this process,    the previous powder was sieved to two groups: one containing the particles between    40-60&#956;m and the other the ones between 22-40&#956;m. Then the feeding rate    was maintained at 1-3rpm, the temperature at 750°C and two different pressures    were used 35-40bar and 32-35bar. The transversal cuts are shown in Figure 11    for 40-60&#956;m and Figure 12 for 22-40&#956;m and the respective microstructures    in Figure 13 and Figure 14. The coatings properties are represented in Table    4. It can be seen that, thanks to the sieved powder, all the coatings present    a more uniform structure with less voids and porosity. When comparing the results    for both powder groups, the coatings with higher particle size are rougher and    a bit thicker, but again the hardness is less uniform. The denser structure    resulting from the smaller particle size, together with its uniformity, makes    the size distribution between 22-40&#956;m the best, of the ones tested, for    cold spray.</p>      <p>&nbsp;</p>      <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f11.jpg" width="473" height="230"></p>         
<p><b>Fig. 11</b> - SEM micrograph of the titanium coating after the powder was    sieved and using the fraction 40-60µm. Number 9 corresponds to a pressure of    [35,40]bar and 10 to [32,35]bar.</p>      ]]></body>
<body><![CDATA[<p>&nbsp;</p>      <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f12.jpg" width="474" height="231"></p>      
<p><b>Fig. 12 - </b>SEM micrograph of the titanium coating after the powder was    sieved and using the fraction 22-40µm. Number 11 corresponds to a pressure of    [35,40]bar and 12 to [32,35]bar.</p>      <p>&nbsp;</p>      <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f13.jpg" width="354" height="269"></p>      
<p><b>Fig. 13</b> - Optical micrograph of the coating number 10 microstructure    after etched with Keller's reagent.</p>      <p>&nbsp;</p>         <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f14.jpg" width="354" height="270"></p>      
<p><b>Fig. 14</b> - Optical micrograph of the coating number 12 microstructure    after etched with Keller's reagent.</p>      <p>&nbsp;</p>      ]]></body>
<body><![CDATA[<p><b>Table 4</b> - Coating properties for the optimized conditions.</p>     <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05t4.jpg" width="472" height="142"></p>        
<p>&nbsp;</p>      <p>And once again, comparing the two used pressures, the highest pressure results    in a lower coating thickness and in higher porosity proving that the 30-35bar    is the ideal value for the deposition of titanium onto these aluminium substrates.    Having this in mind, slightly modified adhesion tests, but following the ASTM    C-633 standard [<a name="top19"></a><a href="#19">19</a>], were conducted in    order to determine the bonding strength. The test consists of gluing a cylindrical    coated specimen with a resin to an uncoated sand-blasted specimen, as it can    be seen in Fig. 15. The obtained results are shown in  Table 5.</p>      <p>&nbsp;</p>         <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f15.jpg" width="254" height="251"></p>      
<p><b>Fig. 15</b> – Set-up for the adherence test.</p>      <p>&nbsp;</p>      <p><b>Table 5</b> – Adhesion test results for the conditions 10 and 12.</p>      <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05t5.jpg" width="450" height="153"></p>         
]]></body>
<body><![CDATA[<p>&nbsp;</p>      <p>The optimum bond strength for a coating is given whenever the failure occurs between the glued surfaces (coated and non-coated surfaces). The used glue resists approximately 70MPa and none of the titanium coatings was able to endure such value. All the coatings exhibited adhesive failure since their rupture was by the substrate/coating interface. The tensile strength average value is very close for both the subjected coatings and it is over the 30MPa, normal value for the plasma-sprayed titanium coatings. However, the values vary between 30MPa and 39MPa, and this last value is a very good result. So, further optimization should be conducted in order to dislocate the average tensile strength value closer to 40MPa.</p>      <p>Once the main goal is to reach a fully dense coating, further optimization    was conducted by removing all the porous area. Figure 16 shows coating number    12 after the removal of the external porous layer. The resulting thickness was    240 ± 2µm and the porosity was reduced to 0.05%. The coating presented a superficial    hardness of 281 ± 40 HV. This value is higher than the previous result for coating    12 since there is more resistance to deformation because the coating is more    compact.</p>      <p>&nbsp;</p>         <p><img src="/img/revistas/ctm/v22n1-2/22n1-2a05f16.jpg" width="380" height="273"></p>      
<p><b>Figure 16</b> - Coating 12 after removing of the porous zone</p>      <p>&nbsp;</p>          <p><b>4. Conclusions</b></p>      <p>Concerning the main objectives proposed at the beginning and in agreement with    the experimental results following the factorial analysis, it can be concluded    as following:</p>      <blockquote>       ]]></body>
<body><![CDATA[<p>&#9679 Principally and most importantly, it was easily and fast obtained      a dense pure titanium coating onto aluminium 7075, with thickness higher than      300µm and no microstructural changes. </p>       <p>&#9679 The effects of gas temperature, gas pressure, and powder feeding rate      on cold sprayed pure titanium coatings onto aluminium substrates were investigated.      All resulting coatings were characterized in terms of their microstructures,      coating thickness and porosity and, micro-hardness. The best set of parameters      was chosen and the corresponding coating was deeper characterized regarding      its hardness profile, phase composition and particle distribution. </p>       <p>&#9679 The parameter that influences more the coating thickness, rising it,      is the feeding rate. For the same feeding rate, the coating thickness increases      with the temperature and decreases with the pressure. Coatings over 300µm      thickness were easily achieved through cold spray.</p>       <p>&#9679 For titanium deposition, higher temperature results in a denser coating      while high pressure (for the used combination of parameters) increases the      porosity due to an erosion effect provoked by the too high particle velocities.</p>       <p>&#9679 Mainly, temperature and pressure affect the plasticity of the particles:      the higher the temperature is for the same pressure value, the more plastic      will be the material and there will be less rebounding; on the other hand,      for a same temperature, a higher pressure can be favourable for a better disposal      of the particle to adhere to the substrate or a former bonded particle but,      above a specific value, it can cause a ballistic effect leading to erosion,      which in our case succeeded at 35-40bar.</p>       <p>&#9679 The particle size distribution is of greater importance in the cold      spray process. A high size distribution leads to non-uniform coatings regarding      thickness, porosity and hardness, and makes the process non-reliable since      particles can either reach or not the critical velocity, and depending on      the main fraction of the powder that composes the coating, the properties      will vary a lot. When the distribution is narrower, the process becomes reproducible,      and the coating properties become more homogeneous.</p>       <p>&#9679 A powder with higher particle size, but narrow distribution, results      in a thicker coating when compared with a powder of smaller particle size.      However, the coating’s properties are less uniform.</p>       <p>&#9679 Regarding the bond formation in cold spray, were found results that      support either the occurrence of a solid-state diffusion with adiabatic shear      instabilities. The bonding strength of the deposited coatings was around 34MPa      with high potential to increase to 40MPa.</p>       <p>&#9679 After optimization, the cold spray process when compared to the conventional      thermal spray techniques, results in coatings with very good properties and      cost-time effective (higher coating thickness can be achieved in less time      and with less money investment), making it ideal for industrial applications.    </p>       <p>&#9679 When the external porous layer is mechanically removed, a fully dense      coating is obtained.</p> </blockquote>     ]]></body>
<body><![CDATA[<p>&nbsp;</p>      <p><b>Acknowledgements</b></p>      <p>The authors are grateful to the Generalitat de Catalunya (Departament de Salut) for the project BARCINO and for the project 2009-SGR 00390, as well as the Ministerior de Ciencia e Innovación for the MAT2009-10827 project. Maria Barbosa wants specially to thank the Thermal Spray Centre-UB for her grant during her stay in the research group.</p>      <p>&nbsp;</p>      <p><b>References</b></p>      <p><a name="1"></a>[<a href="#top1">1</a>]    A. Beuthner, No Vacuum Plasma published    in the Fraunhofer Magazine 1, 2002, pp. 46-47</p>      <p><a name="2"></a>[<a href="#top2">2</a>]     K. Kim, et al., Grain refinement    in a single titanium powder particle impacted at high velocity, Scripta Materialia,    51, 2008, pp. 768-771</p>      <p><a name="3"></a>[<a href="#top3">3</a>]     T. Novoselova, et al., Experimental    study of titanium/aluminium deposits produced by cold gas dynamic spray, Surface    and Coatings Technology, 200, 2006, pp. 2775-2783</p>      <p><a name="4"></a>[<a href="#top4">4</a>]     W. Wong, et al., Effects of gas    temperature, gas pressure and particle characteristics on cold sprayed pure    titanium coatings, Thermal Spray 2009: Proceedings of the International Thermal    Spray Conference, pp 213-236</p>      <!-- ref --><p><a name="5"></a>[<a href="#top5">5</a>]     G. Bae, et al., Bonding features    and associated mechanisms in kinetic sprayed titanium coatings, Acta Materialia,    57 (19), 2009, pp 5654-5666&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;[&#160;<a href="javascript:void(0);" onclick="javascript: window.open('/scielo.php?script=sci_nlinks&ref=146986&pid=S0870-8312201000010000500001&lng=','','width=640,height=500,resizable=yes,scrollbars=1,menubar=yes,');">Links</a>&#160;]<!-- end-ref --><p><a name="6"></a>[<a href="#top6">6</a>]     S. Klinkov et al. Cold Spray Deposition:    Significance of Particle Impact Phenomena. Aerospace Science and Technology,    10, 2005, vol. 9, no. 7, pp. 582-591</p>      <p>[<a name="7"></a><a href="#top7">7</a>]     H. Wang, et al., Effect of Process    conditions on microstructure and corrosion resistance of cold-sprayed Ti coatings,    Journal of Thermal Spray Technology, 17 (5-6), 2008, pp 736-741</p>      <p><a name="8"></a>[<a href="#top8">8</a>]     T. S. Price, et al.. Effect of    Cold Spray Deposition of a Titanium Coating on Fatigue Behavior of a Titanium    Alloy. Journal of Thermal Spray Technology, 15, 2006, pp. 507-512</p>      <p><a name="9"></a>[<a href="#top9">9</a>]     V. K. Champagne, The cold spray    materials deposition process: Fundamentals and applications. Woodhead Publishing    in Materials, 2007</p>      <p>[<a href="#top10">10</a>]  J. Pattison et al., Standoff distance and bow shock    phenomena in the Cold Spray process. Surface &amp; Coatings Technology, 202,    2008, pp. 1443-1454</p>      <p>[<a href="#top10">11</a>]   F. Raletz et al., Critical particle velocity under    cold spray conditions. Surface &amp; Coatings Technology, 201, 2006, pp. 1942-1947</p>      <p>[<a href="#top10">12</a>]   M. Grujicic et al., Adiabatic shear instability    based mechanism for particles/substrate bonding in the cold-gas dynamic-spray    process. Materials and Design, 25, 2004, pp. 681-688</p>      <p><a name="13"></a>[<a href="#top13">13</a>]  C.-J. LI and W.-Y. Li, Deposition    characteristics of titanium coating in cold spraying., Surface and Coatings    Technology, 167, 2003, pp. 278-293</p>      <p><a name="14"></a>[<a href="#top14">14</a>]    L. Ajdelsztajn et al., Synthesis    and mechanical properties of nanocrystalline Ni coatings produced by cold gas    dynamic spraying. Surface &amp; Coatings Technology, 201, 2006, pp. 1166-1172</p>      <p><a name="15"></a>[<a href="#top15">15</a>]    T. H. Van Steenkiste et al.,    Kinetic spray coatings. Surface and Coatings Technology, 111, 1999, pp.62-71</p>      ]]></body>
<body><![CDATA[<p><a name="16"></a>[<a href="#top16">16</a>]   B. Jodoin et al. Effect of particle    size, morphology, and hardness on cold gas dynamic sprayed aluminum alloy coatings.    Surface &amp; Coatings Technology, 201, 2006, pp. 3422-3429</p>      <p><a name="17"></a>[<a href="#top17">17</a>]   S. H. Zahiri, et al., Elimination    of porosity in directly fabricated titanium via cold gas dynamic spraying. Journal    of Materials Processing Technology, 209, 2009, pp. 922-929</p>      <p><a name="18"></a>[<a href="#top18">18</a>]  Y. Xiong et al., Dynamic amorphization    and recrystallization of metals in kinetic spray process. Applied Physics Letters,    92, 2008</p>         <p><a name="19"></a>[<a href="#top19">19</a>]    Unpublished results of the Thermal    Spray Centre, University of Barcelona, 2009</p>     <p>&nbsp;</p>     <p><b>Note</b></p>     <p><a name="a0"></a>[<a href="#topa0">a</a>] Figure 16 shows a CPT coating (Coating    12) after removal of the external porosity layer. </p>     <p>&nbsp;</p>      <p><a name="0"></a><a href="#top0">*</a> <a href="mailto:maria.manuel.barbosa@iws.fraunhofer.de">Maria.Manuel.Barbosa@iws.fraunhofer.de</a></p>         ]]></body><back>
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<source><![CDATA[Acta Materialia]]></source>
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