Contents. Polymer Powders for Selective Laser Sintering (SLS) the special position of PA12
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2 Contents Polymer Powders for Selective Laser Sintering (SLS) Introduction SLS powders SLS powders SLS powders Inspire, AM and SLS current market situation the special position of PA12 the future prospects
3 Introduction inspire AG Competence centre for the Swiss Industry regarding production technique and tooling. Founded on an initiative of ETH-Zürich and machine building industry. Approved as ETH-research annex institute (non-profit foundation). ETH inspire Industry SME Universities of applied science Basic R&D Application driven R&D Technology Development Product development
4 Introduction inspire AG Inspire mimic the Fraunhofer model (Germany) - production technology ETH Zurich Building Empa St.Gallen, icams Technopark Zurich, Headquaters Fields of activity / institutes - iwf-processes: Grinding, Cutting, EDM, - iwf-machines: Process- and machine development - iwf-micromachining: Laser- & micro fabrication - icams: Additive Manufacturing (SLS, SLM) - ipdz: Design for AM & CAD - ics: Composite-Structures - icmi: Material integrity - ifa: Energy - ivp: Virtual production / sheet metal forming
5 Introduction Additive Manufacturing Source: additively.com
6 Introduction Selective Laser Sintering
7 Contents Polymer Powders for Selective Laser Sintering (SLS) Introduction Inspire, AM and SLS SLS powders current market situation SLS powders the special position of PA12 SLS powders the future prospects
8 SLS Materials current market situation total: Polymer (Global) vs. SLS = : 1 PA: PA12 (Global) vs. SLS = : 1
9 SLS Materials current market situation company PA12 nature PA12 filled PA11 nature PA11 filled Other types 3D-Systems (USA) TPE, PS 9 EOS (D) TPE, PS, PEK 19 Arkema (F) ALM (USA) PA6, TPE(2), PS ExcelTec (F) Windform (I) total 32 PA12 filled 39% PA11 unfilled 9% PA11 others PA11 filled17% TPE 6% PA12 unfilled 20% others 15% PU 3% PA6 2% PP 2% PE 1% PEEK 1% Solvay (NL) PA6 1 Lehmann&Voss (D) TPU 1 Diamond Plastics (D) PE, PP 2 Rowak (CH) TPE 1 total PA12 filled 10% PA12 unfilled 85%
10 SLS Materials current market situation Duraform PA / PA 2200 Orgasol Invent Smooth titanium dioxide glass beads aluminium powder carbon fibres mineral fibres PA12/carbon fibres blend
11 such as selective laser sintering (SLS) and high-speed sintering (HSS). Fiber composite materials represent another growth field. SLS Materials current market situation Polyamide 12 powders are an ideal matrix for thermoplastic composites made of fiberglass, carbon fibers, and aramid or steel fibers. Applications can be found in the automotive and oil drilling industry, the sports sector and in orthopedics. VESTOSINT is a modified PA12 powder that is manufactured at the Marl site from a polyamide granulate, using a proprietary Evonik process. Capture: Air duct component for an engine compartment, manufactured with the use of a 3D printing process and VESTOSINT.
12 Contents Polymer Powders for Selective Laser Sintering (SLS) Introduction Inspire, AM and SLS SLS powders current market situation SLS powders the special position of PA12 SLS powders the future prospects
13 SLS powders basic understanding Powder Ageing 5 main topics: Particle Reflection Transmission spherical Optics Shape spattered plane Latent heat Adsorption (10.6 µm) Expansion coefficient Heat capacity Humidity Surface precipitation spray drying cryo-milling Manufacturing hackly Thermal melting oxidation Sintering Window crystallisation Conductivity of heat Homopolymer bulk density tap density recyclability Copolymer Distribution Flowability Rheology Chemistry Surface tension η 0 (melt viscosity) SLS Material > Thermal behavior - sintering window > Particle - spherical - smooth surface > Powder - distrib. (20-80 µm) > Rheology - low zero viscosity > Optical properties - absorption 10.6 µm Requirements and influence factors of a laser sintering material
14 SLS powders distribution Evonik (Vestosint ) Arkema (Orgasol ) EOS (D) PA2200/2201 PA D Systems (USA) Duraform PA DuraForm PA Arkema (F) Orgasol Invent Smooth Orgasol Invent Smooth µm µm µm 100 µm 100 µm 100 µm
15 SLS powders particle shape Evonik (Vestosint ) Arkema (Orgasol ) EOS (D) PA2200/2201 Production: Precipitation 3D Systems Duraform PA Arkema Orgasol Invent Smooth Production: Polymerisation
16 SLS powders particle shape particle as spherical as possible! powder rheology (flowability / fluidisation)! milled powders poor flowability and poor powder density (part density!)
17 SLS powders Synthesis synthesis (polycondensation) of polyamide 12 (PA 12) O H C N H O + H 2 O H N C OH (CH 2 ) n Lauryl lactam polyamide 12 PA12: ring opening polyaddition of Laurinlactam: = reactive end groups -NH 2 and -COOH n post condensation during SLS processing increasing chain length increasing melt viscosity
18 SLS powders polymer chain length H H O H O N (CH 2 ) 11 C OH + H N (CH 2 ) 11 C OH n m T, t, Δp H2 O K p,t = [chain(m+n)] H 2 O [chain(m)] [chain(n)] H H O N (CH 2 ) 11 C OH + n+m H 2 O Chemical equilibrium depends on Δp and T SLS provides best conditions for successful post condensation T > 100 C; dry N 2 atmosphere drying chamber!
19 SLS powders molecular weight increase ΔT, t - H 2 O vapor
20 SLS powders part properties Laser mirror COOH top layer NH 2 CONH COOH NH 2 COOH 2 nd layer new part CONH NH 2 3 rd layer powder Inter-layer bonding intra-layer bonding SLS building chamber
21 SLS powders thermal properties thermal situation in building chamber
22 SLS powders thermal properties Sintering window differs for every PA12 type! comparison of PA12 SLS-powders comparison with standard injection molding PA12 (Grilamid L20)
23 Contents Polymer Powders for Selective Laser Sintering (SLS) Introduction SLS powders SLS powders SLS powders Inspire, AM and SLS current market situation the special position of PA12 the future prospects
24 SLS Materials The future prospects It s all about powder production Powder production by precipitation Duraform/PA2200 (PA12) Technology summary 1. Dissolve polymer (PA12) in solvent (ethanol) under temperature and pressure 2. Reduce pressure to let polymer precipitate from solution 3. Remove solvent by evaporation 4. Collect powder Powder production by melt blending icopp Technology summary 1. Mix polymer with a sufficiently large quantity (water-)soluble resin 2. Melt blending 3. Remove soluble phase with solvent 4. Evaporate solvent and extract particles Powder production by milling/grinding Duraform Flex powder Rilsan PA11 powder PEEK Optima Many others (non-commercialized) Technology summary 1. Cool polymer to far below T M and/or T g with LN 2 2. Grind in specialized mill 3. Collect and optionally sieve powder Powder production by emulsion polymerization Orgasol Invent Smooth PA12 Technology summary 1. Start with an incompatible mixture of monomer and solvent 2. Add surfactant and stir 3. Start polymerization 4. Evaporate solvent and extract powder
25 SLS Materials The future prospects Production Method Powder quality Ease of use Cost Precipitation + - Milling/grinding Emulsion Polymerization Melt blending/coextrusion Who s next?
26 SLS Materials Bridging the gap - icopp PP-material (SLS) with outstanding properties regarding ductility and EaB
27 The team inspire AG, icams Prof. K. Wegener Scientific Lead Chair of IWF ETH Zürich M. Schmid R&D-SLS A. Spierings R&D-SLM F. Amado process understanding and simulation M. Vetterli influence of powder on SLS-parts / surfaces R. Kleijnen new powders and production processes M. Cloots micro structures and process simulation T. Bauer process engineering / materials characterisation P. Stoll new applications and functional structures
28 Thank you! Questions?
Manfred Schmid 1 and Konrad Wegener 2
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