In Proceeding of International Conference on Recent Anvances in Materials and Processing Dec. 15-16, 2006, PSG-tech.

Coimbatore, INDIA

ADVANCES IN MATERIALS FOR POWDER BASED RAPID PROTOTYPING Prashant K. Jain1 K. Senthilkumaran1 Pulak M. Pandey2 P. V. M. Rao3
1

Research Scholar

Assistant Professor

Associate Professor

Mechanical Engineering Department Indian Institute of Technology Delhi, New Delhi

2

pmpandey@mech.iitd.ac.in

Abstract: Rapid Prototyping (RP) is two decade old technology to quickly produce tangible objects directly from a 3D CAD model and is being used to shorten and simplify the product development cycle for many applications including aerospace, automobile and home appliances etc., It involves adding material successively, in layers, to create a solid of a predefined shape. Over the years, RP has evolved from producing prototypes for form, fit and functional testing to producing final end products for functional use. Since the presentation of first commercial application in last decade, a large number of processes have been developed. Present day commercial systems use various materials that range from polymers, metals, metal-polymer composites, ceramics and sand. As the growing number of new applications constantly motivate in developing new materials, it is essential to study the feasibility of new materials suitable for layered manufacturing. The properties of the material, particle size, fusibility of powder particles and thermal and optical characteristics are the bottlenecks in achieving required mechanical properties, feature resolution, accuracy and surface quality of the end product. In this paper, recent developments in materials for powder based layered manufacturing is reviewed and emphasize is given on issues and challenges in developing new materials and methods to meet high standards of part quality. Also recent research and accomplishments in processing bio-materials, heterogeneous materials and direct tools are discussed. Keywords: Rapid Prototyping, Selective Laser Sintering, Materials

1.0 INTRODUCTION In 1987, Carl Deckard at University of Texas found that polymer powders can be selectively sintered using a laser beam to create complex solid objects. Also the development of computers and CAD systems in the past decade made this technology commercially viable and in the recent past researchers found this technology suitable for any type of material which can be pulverized in the form of powders [1]. Due to the varied material capabilities, Selective Laser Sintering (SLS) process now stands as an alternative to conventional manufacturing techniques. Because of the time compression between product conceptualization to realization, these technologies are sometimes referred to as Rapid Manufacturing [2]. Because of the wide range of materials it can process, SLS is superior to other Rapid Manufacturing techniques [3]. The materials include wax, cermet, ceramics, nylon/glass

composite, metal-polymer powders, metals, alloys, steels and polymers [4]. A review of materials processed by SLS has been done by Kruth et al. [5]. Initially Polycarbonate powders (Bisphenol-A polycarbonate) were used. Later Nylon and nylon composites have become industry standards for prototypes and functional models due to high wear and chemical resistance [6]. Researchers tested the use of a sacrificial polymer binder and found that any material can be combined with a low-melting-point material which will serve as glue/binder in SLS. Metal systems were studied for laser sintering since rapid tooling needed accurate metal dies and moulds. Recent research efforts [7-16] showed the capability to process high temperature, high performance materials, making this process comparable to conventional manufacturing techniques in producing metal components with almost same mechanical properties by successfully processing nickel base
1

superalloys, titanium alloys and superalloy cermets into functional components for automotive and aerospace applications. SLS also processes bio-materials for fabricating scaffolds in tissue engineering scaffolds. Layer-bylayer additive fabrication in SLS allows construction of scaffolds with complex internal and external geometries. Moreover, virtually any powdered biomaterial that will fuse but not decompose under a laser beam can be used to fabricate scaffolds. SLS enables fabrication of anatomically shaped scaffolds with varying internal architectures, thereby allowing precise control over pore size, porosity, permeability, and stiffness. Control over these characteristics may enhance cell infiltration and mass transport of nutrients and metabolic waste throughout the scaffold. SLS also allows for the fabrication of biphasic scaffolds that incorporate multiple geometries into a single scaffold, allowing for ingrowth of multiple tissues into a single scaffold structure. Recent advances focus on processing of Polycaprolactone, hydroxyapatite by SLS for bone and cartilage tissue engineering [17]. This paper presents advances in above mentioned fields and the paper is organized into different sections based on the different materials. These materials are namely polymers, wax, cermets, ceramics, nylon/glass composite, metal-polymer powders, metals, alloys. Research issues in processing of bio-materials and functionally graded material (FGM) for bio medical applications have been dealt in last section. 2.0 MATERIALS FOR POWDER BASED RP SLS can be used to process almost any material, provided it is available as powder and that the powder particles tend to fuse or sinter when heat is applied.
Metal & Alloys

polymer binder) to the basic powder. Figure 1 shows the wide range of materials SLS can process. 2.1 Polymers The initial materials used in SLS are polymers which are materials made up of long-chain molecules formed primarily by carbon-to-carbon bonds. Mostly, three types of polymers are used in engineering: thermoplastics; thermosetting plastics; and elastomers. Most polymers used in SLS process are thermoplastics. Thermoplastics can be recycled in SLS, thus saving material. Generally, thermoplastic polymers can be classified into two types: amorphous and crystalline. Amorphous material has chain molecules arranged in a random manner like in polycarbonate (PC). Crystalline material has chain molecules arranged in an orderly structure like in nylon. Amorphous polymers are able to produce parts with very good dimensional accuracy, feature resolution and surface finish (depending on the grain size). However, they are only partially dense parts. As a consequence, these parts are only useful for applications that do not require part strength and durability. Typical applications are SLS masters used for manufacturing silicone rubber and cast epoxy moulds [18]. The first sintering model developed for processing of polycarbonate shows the effect of energy density on the sinterability of polycarbonate powder beds [19]. The densification and accuracy of PC parts are most sensitive to changes in activation energy and heat capacity of the amorphous polymer [20]. Also the accuracy of parts depends mostly on the process parameters as well [21]. Semi-crystalline polymers on the contrary, can be sintered to fully dense parts with mechanical properties comparable to injection moulded parts [5]. Prototypes made by these materials widely employed where strength and wear resistance is the main consideration. Typical applications of these materials are fully functional prototypes and sometimes as the final product. Figure 2 shows some of the nylon parts.

Single Component Two Component

Alumide Cu PA Amorphous Semi Crystalline With Glass & Carbon reinforcement

Cermets

Alumina + Binders

Alumina SiC

Polymer

Ceramic

Figure 1 Materials for SLS Powders that depict low fusion or sintering properties can be laser sintered by adding a low melting temperature binder material (typically a

Figure 2 Some polyamide parts produced by SLS

Shrinkage of these semi-crystalline polymers during processing is typically 3-4 per cent [22] and depends on the process parameters, which complicates production of accurate parts. New grades of nylon powders (i.e. Duraform PA12, Fine Polyamide, PA2200) even yield a resolution and surface roughness close to those of PC, making PA also suited for casting silicone rubber and epoxy moulds. Other polymer-based materials available commercially are acrylic styrene for investment casting and an elastomer for rubber-like applications [23]. Shi et al. [24] studied the relationship between the crystallinity of the polymer material (Nylon 12) and the accuracy of the SLS part. They found the crystallization rate, which is closely correlated with crystallinity, greatly affects the accuracy and precision of the SLS part. Tontowi and Childs [25] measured density of commercially supplied powders, known as Duraform (nylon-12_ & Protoform (glass filled nylon-11) and studied the effect of varying bed temperature on the density of sintered parts produced by the SLS process. They developed simulation model for density prediction based on experimental results. Gibson and Shi [26] comprehensively analysed the relationship between powder properties, fabrication parameters and the mechanical properties of nylon SLS parts. Mechanical properties of SLS parts are influenced by powder properties and fabrication parameters. Recently, Ajoku et al. [27] compared compressive strength of laser sintered and injection moulded Nylon-12 parts and developed finite element model for compressive strength. The modulus of the laser sintered Nylon- 12 is 10% less than that of the injection moulded Nylon-12 Modulus. This difference is as a result of the porosity within the laser sintered part which can be inferred from figures 3 and 4. During polymer laser sintering, pores can arise as a result of uneven heat distribution within the build area, inadequate heat supply from the laser and insufficient process temperatures [27]. These pores do not have any definite size, shape and location within a sintered component.

Figure 4 SEM showing no porosity within a crosssectional area in an injection moulded part [27]. 2.2 Reinforced and Filled Polymers Polymer powders can be easily reinforced with other materials in order to further improve their mechanical and thermal properties. Several grades of glass fibre reinforced PA powders are readily available the market [28]. The part fabricated from glass filled polyamide (PA3200 GF) has excellent mechanical properties and high accuracy. Typical applications of these materials are housings and thermally stressed parts. Childs and Tontowi [29] measured density of glass filled nylon-11 and simulated the effect of varying bed temperature on the density of sintered parts. DTM Corporation (Austin, USA) introduced in mid-1998, copper polyamide, which is a thermally conductive composite of copper and plastic and can be used to create tooling for short runs of production equivalent plastic parts. Copper polyamide is suitable for injection moulded inserts to mould around 100400 parts in polyethylene (PE), polypropylene (PP), glass filled PP, polystyrene, ABS, PC/ABS, and other common plastics. Lower material strengths are the limitation in application of Copper polyamide moulds. Recently, Windform XT is introduced into commercial market which is based on a carbon-filled polyamide and produces black parts with a smooth finish and a sparkling appearance [30]. It has a low density and a high tensile strength and tensile modulus. Electro Optical Systems (EOS) has also announced its carbon filled polyamide powder called CarbonMide having almost same characteristics that of Windform XT [31]. 2.3 Metals and Alloys In usual practice, SLS allows producing metallic parts using some kind of sacrificial polymer binder. Nowadays, direct sintering of metallic powders without the use of a polymer binder is also investigated. This further enlarges the range of powders used in SLS. Early attempts [32] to SLS process metallic powders and powder blends of copper, lead, tin, and zinc proved to be unsuccessful because of balling. As the increase in energy density causes a larger degree of melting, causing material to

Figure 3 SEM showing porosity within a crosssectional area in a laser sintered part [27].

form spherical balls whose diameters tend to increase with further increase in energy density as shown in figure 5. Since the molten metal is fully contained by loose powder rather than a fully dense material, the tensile traction on the melt is not sufficient to confine it to a layer wise geometry. A two-phase powder approach was used to overcome balling effects [33]. This was achieved using a pre-alloyed single phase powder system in which melting occurs over a range of temperature, or a powder blend of two phases with different melting temperatures. In the former case, laser processing parameters are manipulated so that only partial melting occurs.

Figure 5 Balling effect found on Ni alloy on quartz substrate [33] DTM Corporation has developed a process that applies polymer-coated steel powders (1080 Steel, 316 or 420 Stainless Steel particles coated/mixed with a thermoplastic /thermoset material) for the SLS of metal parts. During laser sintering, the polymer melts and acts as a binder for the steel particles. This binder needs to be debinded to get the green part. After debinding, the porous steel part is infiltrated with copper or bronze. Over the years, DTM Corporation has developed RapidSteel powder, composed of 60 percent 420 Stainless Steel and 40 percent Bronze, for which debinding and infiltration can be done in a single furnace cycle of about 24 hour under pure Nitrogen. These developments give better material properties of the final SLS parts such as strength, hardness, machinability, weldability, wear rate and thermal conductivity [35].

Figure 6 Direct laser sintered 3D metal parts [61].

LaserForm ST-100 (420 Stainless Steel based powder), is the latest tooling material system offered to replace RapidSteel 2.0 and Copper Polyamide powders. LaserForm ST-100 tooling is reported to be fully dense after LS with surface roughness of 5 m Ra. RapidTool moulds have been successfully employed in both plastic and wax injection moulding [36]. Reports claim that complex moulds are produced in less than 2 weeks and are capable of producing 50,000 to 100,000 parts [37]. EOS avoids the use of polymer binder and uses direct sintering of metal powders with a low melting point, i.e. bronzenickel based powders (EOS-Cu 3201 containing CuSn, Cu-P and Ni particles) developed by Electrolux Co. [38]. After SLS, the part is infiltrated with epoxy resin to fill in the pores. Hence the final part is a bronze-epoxy composite, rather than a plain metallic part and its mechanical and thermal properties are limited. Infiltration with a metal like copper or bronze is not possible in this case, since the green part would melt during infiltration. The direct metal laser sintering (DMLS) process and a new powder (EOS-DMLS Steel 50-V1 containing steel, Cu-P and Ni particles) yielding improved mechanical properties was introduced in the market by EOS [39]. Some of the parts produced by DMLS is shown in figure 6. Solid state sintering is a thermal process which occurs at a temperature between its re-crystallization and melting temperature. The driving force for binding is a physical diffusion of metal atoms from one particle to another. This is inherently a slow phenomenon and illustrates the main drawback of solid state sintering for DMLS [40]. Studies show that the average interaction time from the laser beam with the particles is too much short to initiate sintering. In this direction, Schueren and Kruth [40] examined different metal powder mixtures of (Cu, Fe, Sn) for sinterability. The best results are obtained with a mixture of Fe and Cu powders. Zhu et al. [41] demonstrated the feasibility of producing Cu-based metal parts directly by SLS using various metal systems such as CuSn, bronzeNi, Cu-solder and CuFe. Zhu et al. [42] showed that the ratio of Fe and Cu significantly influences part distortion in a FeCu system. Tungsten articles act as an obstacle to affect the accuracy of the part size because the unmelted tungsten particles have a large friction to impede rearrangement. Wang et al. [43] showed that the WC-Co system can be processed over a relatively wide range of processing parameters compared to a Fe-Cu powder mixture. This is due to the good absorption characteristics of WC and Co materials [44]. Simchi and Pohl [45] investigated the effect of short hatch lengths on warpage in SLS of iron powder. They have shown that sintered density was higher when using short vector length. It should be noted that the scan vector length influences the development of thermal stresses as well. These residual internal stresses are responsible for reduced

part performance as well as warpage, loss of edge tolerance and even delamination of layered deposited parts. On the other hand, the effect of powder bed temperature on the sintered density was not conspicuous since the preheated condition was not high enough. Although it influences the thermal stresses developed during processing. 2.4 Ceramics Ceramics are hard, brittle, very high melting points with low electrical & thermal conductivity, good chemical and thermal stability, and high compressive strength. They exhibit both ionic and covalent bonding. The most common ceramics used in RP are Al2O3, SiO2, and ZrO2 [46]. Few researchers [47-49] have attempted to produce directly ceramic parts without polymer binder material. The absence of any binder element makes the ceramic laser sintered part very fragile and viable to breakage. Due to the short reaction time involved in SLS, solid state sintering is not feasible. SLS has been used to produce ceramic parts by using either ceramic particles coated with binder or a mixture of ceramic and binder particles. Alumina parts were made using the laser sintering followed by an infiltration step using an alumina colloid. After sintering maximum strengths obtained were around 14 MPa due to the low sintered densities of about 55% [47]. SLS has been used to produce ceramic investment casting molds. Partially stabilized Zirconia molds for Titanium casting were made by SLS of stabilized Zirconia which was then infiltrated with unstabilized Zirconia before being sintered [48]. Aluminum with SiC is light weight, high conductivity and strength, low thermal expansion coefficient and sufficiently high wear resistance. Thermal conductivity, as the next important property, can be changed within a wide range by addition of different amounts of SiC particles to the starting powder mixture. Because of these beneficial properties, several parts are produced from AlSiC composites, mainly for the automobile industry, and for electronic packaging applications [49]. 2.5 Foundry Sand Now sand powders are commercially available that can be laser sintered to produce foundry sand moulds. DTM offers Zirconium and Silicon sand commercial name SandForm ZrII and SandForm Si. SandForm Si, used for Al castings, is based on silica, and has a low density. SandForm ZrII is used for Al and Fe castings and its binder system matches silica [5]. The LASERCON coated sand offers by EOS have a composition of 96.8% quartz sand and 3.2 % resin. The mean grain dimension is 170 microns, and density 1550 kg/m3. Figure 7 shows a core made out of EOSINT machine [28].

Figure 7 Left cylinder head of V6-valve car Sand Moulding was Core Produced on EOSINT S 700 Direct Croning System [38] 2.6 Functionally graded materials Functionally graded material (FGM), also called heterogeneous materials, are a new generation of engineering materials wherein the micro structural details are spatially varied through non-uniform distribution of the reinforcement phase(s), by using reinforcement with different properties, sizes and shapes, as well as by interchanging the roles of reinforcement and matrix phases in a continuous manner. The result is a microstructure that produces continuously or discretely changing thermal and mechanical properties at the macroscopic or continuum scale. Some primitive FGM objects are shown in figure 8.

Figure 8 Heterogeneous primitives [63]. Functionally graded material has become a subject of research in the material science, composites, and ceramic engineering and metallurgy communities. Processing methods for FGMs have been extensively reviewed by Kieback et al [50]. In the specific context of FGMs involving polymer composites, processing methods include hot iso-static pressure casting, compression molding, and centrifugation. SLS can fabricate such heterogeneous objects. The material deposited can be varied continuously to yield a functionally graded material object with varying material distribution. Some of the studies in processing of polymer composites by SLS have been reported by Zhou et al. [51]. Das and Chung [52]

discussed the fabrication of FGMs by SLS of Nylon11 composites. They built one dimensional FGM with varying compositions of glass bead on nylon 11. They investigated processing of Nylon-based composites with different volume fractions of glass fiber and glass bead reinforcements. They also reported previous attempts of one dimensional FGM part processed by using blend of tungsten carbide & cobalt powders and H-13 tool steel & copper powders. 2.7 Biomaterials As the powders are subjected to low compaction forces during their deposition to form new layers, SLS-fabricated objects are usually porous. This interconnected porosity is a key property requirement in biomedical applications, including artificial bones and tissue engineering scaffolds. Figure 9 shows some of the complex 3D Scaffold designs. The nature and extent of this interconnected porosity can be tailored and controlled effectively to meet different application criteria through material selection and physical design, and owing to the additive nature of the SLS process, control over internal structure is possible.

investigated the development of optimal SLS processing parameters for CAPA6501 polycaprolactone powder using systematic factorial design of experiments. The test scaffolds with designed porous channels were able to achieve a dimensional accuracy to within 3%8% of design specifications and densities approximately 94% relative to full density. 3.0 CONCLUSIONS In this paper current state of the art in processing of different materials through SLS is presented. Studies involving developing new materials and improving the existing materials were discussed. Although many materials have been developed, there is still a need for research into new materials. It should be noted that the SLS process is still a relatively new process and therefore continued development of the technology and understanding of process fundamentals is needed to carry the technique forward. The addition of a secondary material to modify the mechanical properties of polymers is common practice, to ensure materials meet design requirements and are suitable for a wide range of applications. Addition of rigid particles and clay to polymers can produce a number of desirable effects on the mechanical properties of parts. The knowledge of existing materials and the nature of complexity in processing them by laser will be helpful in achieving functional requirements of parts for present and future applications. The future of bio-manufacturing which combines principles of RP and Bio-science can form complicated bio tissue scaffolds, is a potential technology to make artificial organs. 4.0 ACKNOWLEDGMENTS Authors gratefully acknowledge the financial assistance provided by Industrial Research and Development unit of Indian Institute of Technology Delhi to carry out this work. 5.0 REFERENCES [1] Pham, D.T. and Dimov, S.S. Rapid Manufacturing: The technologies and applications of Rapid Prototyping and Rapid Tooling, Springer-Verlag London Limited, 2001. [2] Chua, C.K. and Leong, K.F. Rapid prototyping: Principles and applications in manufacturing, John Wiley and Sons Inc., 1997. [3] Venuvinod, P.K., and Ma, W. Rapid prototyping: Laser based and other technologies, Kluwer Academic Publishers, 2004. [4] Kumar, S. Selective Laser Sintering: A Qualitative and Objective Approach, Jl. Of Manuf., 2003, Vol. 55, pp. 43-47. [5] Kruth, J.P., Wang, X., Laoui, T. and Froyen, L. Lasers and materials in selective laser sintering, Assembly Automation, Vol. 23, No. 4, 2003, pp. 357371.

Figure 9 complex 3D Scaffold designs [62] The porosity also offers an opportunity during postprocessing to introduce additional materials into the object to alter material composition as well as help to control part stability. Polymethyl methacrylatecoated calcium phosphate powders have been successfully processed via SLS and subsequent postprocessing enables to produce strong porous structures [53]. Das et al. [54] investigated the design and fabrication of scaffolds with periodic cellular and biomimetic architectures using nylon and built cubes with 0.8 mm channels and 1.2 mm pillars. Williams et al. [55] designed and fabricated scaffolds of polycaprolactone, a bioresorbable polymer, with the smallest pores being 1.75 mm in diameter. Tan et al. [56, 57] and Chua et al. [58] found micropores formed within the scaffold structure produced via SLS from physically blended Hydroxyapatite (HA)/polyetheretherketone and HA/polyvinyl alcohol composites. Internal porosity with 150 mm average pore size in the SLS-fabricated HA/poly(L-lacide) specimens are also reported [59] . Das et al. [60]

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