Lithographiebasierte Generative Fertigung: Verfahren ... Generative Fertigung: Verfahren,...

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Lithographiebasierte Generative Fertigung:

Verfahren, Anwendungen und Werkstoffe

J. Stampfl

1Mar. 2016 ERFA AM Leoben

Market Volume

Mar. 2016 ERFA AM Leoben Folie 2

Mill

ion

en

Te

ilep

ro J

ah

r

0

500

1000

1500

2000

2500

3000

3500

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

2010

2011

2012

2013

Mio

. USD

Products Services

Worldwide revenues (Million US$).

green: Systeme, blue: Services

Source: Wohlers 2014

Materialverkäufe

Mar. 2016 ERFA AM Leoben Folie 3

Davon: 298Mio$ Photopolymere

160Mio$ Polymere Lasersintern

50Mio$ Metalle Lasersintern

Can we 3D-print it?

Mar. 2016 ERFA AM Leoben Folie 4

Stephansdom 1:400 000

Aerospace Biomedical Industry

nm-scale m-scale

Internet based manufacturing

Mar. 2016 ERFA AM Leoben Folie 5

B2C:

• Thingiverse

• Shapeways

B2B:

• Formerly known as

service provider

(Automotive, Product

Development)

Customized manufacturing

Mar. 2016 ERFA AM Leoben Folie 6

Market: 100.000 aligners per day

Largest use of AMT

Source: Align Technologies

Hearing aid shells

Mar. 2016 ERFA AM Leoben Folie 7

>90% of hearing aid shells are made by AMT

Dilemma of 3D-Printing

Materials

Geometry

Economics

FDMSLS SLAInkjet Printing

-Brittle

photopolymers

Medium surfaces

+Good precision

+Cheap

+Fast

+Polyamide

+Many metals

+Good precision

-Rough surfaces

+Costly systems

-Slow

+ABS

+PLA

-Poor precision

-Rough surfaces

+Very cheap

Medium build

speed

-Brittle

photopolymers

+Good precision

+Good surfaces

+Cheap

+Relatively fast

Mar. 2016 ERFA AM Leoben Folie 8

Additive Manufacturing Technology (AMT)

Mar. 2016 ERFA AM Leoben Slide 9

• Structuring methods:

• Two photon polymerization,

• Digital Light processing

• Benefits of lithography-based AMT:

• High resolution (<100nm)

• Tailoring material properties is easy

• In-vivo-writing

10mm

L-AMT in Wien

Mar. 2016 ERFA AM Leoben Folie 10

TU Wien (Prof. Liska, Prof. Stampfl)• 30 Mitarbeiter AMT Gruppe• >15 Patentfamilien, >70 referierte Journal

Papers, • EU: FP7, H2020, ERC, • National: FFG Leitprojekt, FWF, CD Labor,

Houska Preis• Firmenprojekte Gesamtvolumen >2,25 Mio €:

Lie, CH, D, Il, USA, F

Lithoz GmbH (Keramik)• 90% Exportquote, 25 Mitarbeiter

Cubicure GmbH (Polymere)• 4 Mitarbeiter

Verfahren

Mar. 2016 ERFA AM Leoben Folie 11

DLP

ERFA AM Leoben Folie 12

1

2

3

45

6

1 Light Source (LED 450nm)

2 DMD Chip

3 Optics

4 Coating system

5 Tiltable vat

6 Build platform

Resolution: 40mm

Build-size: 80x45mm²

Build-speed: 10mm/hour

"Lichthärtende Schlicker für die stereolithographische Herstellung von Dentalkeramiken"; US7927538 (B2) 2008

“Device and method for processing light-polymerizable material for the layered assembly of molds”, WO2010045950

“Method and device for generative production of a mould with non-planar layers”, EP2251185 (A1),

“Device and method for processing light-polymerizable material for building up object in layers”, WO2010045951 (A1),

Mar. 2016

L-AMT in Wien

ERFA AM Leoben Folie 13Mar. 2016

Lithoz GmbH

(Weltmarktführer Keramik 3D-Druck)Cubicure GmbH

Förderung Wirtschaftsagentur Wien

Two-photon-polymerization

ERFA AM Leoben 14

Voxel(Width ~ 100 nm)

Sun, H.-B.; Kawata, S.Journal of Lightwave Technology; 21; 624-633; (2003)LaFratta, C. N.; Fourkas, J. T.; Baldacchini, T.; Farrer, R. A. Angewandte Chemie, International Edition; 46; 6238-6258; (2007)

Mar. 2016

Zweiphotonenpolymerisation

Mar. 2016 ERFA AM Leoben 15

TU WienStephansdom

1:400 000

N. Pucher, A. Rosspeintner, V. Satzinger, V. Schmidt, G.

Gescheidt, J. Stampfl and R. Liska, Macromolecules,

42, 6519–6528, (2009).

K. Cicha, Z.Li, K. Stadlmann, A. Ovsianikov, R. Markut-

Kohl, R. Liska, J.Stampfl, J. Appl. Phys. 110, 064911

(2011)

Fast 2PP writing

Mar. 2016 ERFA AM Leoben Folie 16

Resin: Methacrylat

Initiator: R1

Writing speed increase:

From 50mm/s to 5000mm/s

3D CAD Model of race car:

Dimensions of

330x130x100µm3

Precision of ±1µm

Fabrication time 4 minutes

Werkstoffe

Mar. 2016 ERFA AM Leoben Folie 17

Ceramics

Ceramic restorations (crowns, bridges):

• Esthetics

• Mechanical properties

• Process time

AMT for digital dentistry

Christian Dopler Laboratory for

Photopolymers in digital and

restorative dentistry (2012-2019)

Mar. 2016 ERFA AM Leoben Folie 18

Material properties ceramics

[1] Verband der Keramischen Industrie e.V., Brevier Technische Keramik, 2003, p.270

[2] L.L. Hench et al., “Properties of bioactive glasses and glass-ceramics”; pp. 355–363 in Handb. Biomater. Prop. Edited by J. Black and G.

Hastings. Springer US, 1998

[3] R. Felzmann et al, Adv. Engng. Material 2012.

[4] G. Mitteramskogler et al., “Light Curing Strategies for Lithography- Based Additive Manufacturing of Customized Ceramics”, Euromat 2013

[5] R. Gmeiner et al., “Stereolithographic Ceramic Manufacturing of High Strength Bioactive Glass“, accept. & await. publication in Int. J. Appl.

Ceram. Tec., 2014

Material

Al2O3 ZrO2 45S5 Bioglass®

Measured biaxial bending strength

(MPa) 516 [3] 1009 [4] 124 [5]

biaxial bending strength in

literature (MPa) 300-580 [1] 1000 42 [2]

Density (g/cm³) 3,82 5,9 2,7

Relative Density (%) 99,6 99,92 > 99

Solid loading – green parts (vol%) 50 42 47,7

Max. building speed. (mm/h) 9 7 7

Mar. 2016 ERFA AM Leoben Folie 19

Ceramics

Bioglass

Alumina

Zirconia

Mar. 2016 ERFA AM Leoben Folie 20

Polymere

Source: T. Swetly, Capabilities of additive manufacturing technologies (AMT) in the

validation at BMW, Rapid. Tech, Mai 2014

SLA FDM SLA SLS Casting

Ch

arp

y Im

pa

ct S

tre

ng

th [kJ/m

²]

Mar. 2016 ERFA AM Leoben Folie 21

Commercial SLA resins

Mar. 2016 ERFA AM Leoben Folie 22

Commercial SLA resins

Mar. 2016 ERFA AM Leoben Folie 23

Structure-property relations

Properties of photopolymer Increase

crosslink density

Increase

intermolecular

forces

Increase molecular

weight of

monomers

Glass transition temperature Tg ↑ (+) ↑ (+) ↑ (+)

Impact strength (toughness) ↓ (-) ↑ (+) ↑ (+)

Elastic modulus ↑ (+) ↑ (+) ↑ (+)

Polymerization shrinkage ↑ (-) ↔ ↓ (+)

Processability (viscosity) ↔ ↓ (-) ↓ (-)

Reactivity ↑ (+) ↔ ↓ (-)

Better thermo-mechanical properties (Tg, toughness)

Intermolecular bonding (H-binding)

High molecular weight MwDifficulty processing

Mar. 2016 ERFA AM Leoben Folie 24

Monomers & Fillers

spacerN

HO

O

O

O

R

N

H

O

OO

O

R

Polyester UMA

Good thermo-

mechanical properties

low shrinkage

Isobornylacrylate (IBOA):IBOA

Reactive diluent

High Tg

Urethane (meth)acrylate (UMA):

Core-Shell particles (CSPs):

soft core

rigid shell

CSP

Toughening agent

Mar. 2016 ERFA AM Leoben Folie 25

Toughening with CSP

Sample

Nr.

UA

[wt. %]

IBOA

[wt. %]

CSP

[wt. %]

Charpy

[kJ/m²]

Tg tan δ

[°C]

1 88,0 12 - 15,0 69

2 91,0 9 - 39,3 70

3 99,0 1 - 42,1 75

4 86 3 10 57,3 72

Accura X. 37,4 70

Mar. 2016 ERFA AM Leoben Folie 26

Formulation 2M

No redardation

Cheap Synthesis

Mechanical Properties

Unique Advantages

Ductility

Formulation 2M + 20% CTA

Mar. 2016 ERFA AM Leoben Folie 28

The Scientist, 2004

The Economist, 2010

29

Robotization and automation

help to transform emerging

promising technologies into

economically feasible

industries!

Organ Printing

Mar. 2016 ERFA AM Leoben 29

Osteochondral Scaffolds

Mar. 2016 ERFA AM Leoben Folie 30

J-H Shim et al, Biofabrication 8 (2016), 014102

Osteochondral Scaffolds

Mar. 2016 ERFA AM Leoben Folie 31

J-H Shim et al, Biofabrication 8 (2016), 014102

Bovine serum albumin + vinyl ester

Mar. 2016 ERFA AM Leoben Folie 32

J.Torgersen, X.H.Qin, Z.Li, A.Ovsianikov, P.Gruber, R.

Liska and J.Stampfl, Adv. Func.Mat 2013, DOI:

10:1002/adfm.201203880

BSA-SH: Bovine serum albumin macrothiol

GH-VE: Gelatine hydrolisate vinyl ester

Biological materials for 3D-environments

Mar. 2016 ERFA AM Leoben Folie 33

X 25

Y 00

100 mW

X 15

Y 10

330 mW

• X% Bovine serum

albumin

• Y% Gelatine

hydrolisate

• 75% PBS buffer

• 0.5wt% WSPI

• Suitable for in situ

applications

X 16

Y 09

280 mW

500

µm

500 µm

Qin et al., Manuscript in Preparation

Summary

FFG Leitprojekt

• L-AMT führend hinischtlich Präzision und

Auflösung

• Herausforderungen liegen vor allem im

Materialbereich

• Prozesseite hat große Fortschritte gemacht

(Durchsatz, Kosten, Zuverlässigkeit)

• Ziel muss es sein, zu produzieren (Biomed,

Individualisierung, Kleinserien, ..)