NEW DEVELOPMENTS IN ADDITIVE

MANUFACTURING BY
SELECTIVE LASER SINTERING:
APPLICATION TO POLYMER BLENDS
AND FILLED POLYMERS
J.-M. Lopez-Cuesta. M. Batistella. M. Pucci. A. Regazzi
C2MA, IMT Mines Ales, 6 Av. de Clavières 30319 Ales cedex

[Link]-cuesta@[Link]

C2MA
Centre des Matériaux des Mines d’Alès
 C2MA
Centre des Matériaux des Mines d’Alès
OUTLINE

INTRODUCTION

1. SLS MACHINE TECHNOLOGY

2. SLS POWDERS CHARACTERISTICS
3. PROCESSING PARAMETERS AND POLYMER PROPERTIES
4. SLS OF BLENDS AND FILLED PA12
5. FR PA12 SLS COMPOSITIONS
6. FIRE PERFORMANCE OF FR PA12 SLS
7. SLS OF PEBAX COPOLYMER

CONCLUSION
 I INTRODUCTION 3I

POWDER BED FUSION (PBF) :

1 of the 7 families of ADDITIVE MANUFACTURING technologies

PBF Technologies :

- HP multi-jet fusion process (use of a binder, a detailing agent and energy)

- High speed sintering (HSS) (use of a IR absorbing fluid which melts and sinters)
- Selective Laser Sintering

First patent in 1986

University of Texas-Austin
Carl Deckard

[Link]
3
 1. SLS MACHINE TECHNOLOGY 4I

Powders of polymers in the 20-80 µm range are heated to a T lower than melting
or softening and temperature submitted to a laser beam entailing a local sintering
for successive bed of powders

Powders from feeding tanks are spread using specific tools

Laser Sintering with plastics

[Link], Hanser 2018

Roll coating Simple blade double blade cartridge 4

 1. SLS MACHINE TECHNOLOGY 5I

HEAT SOURCES
 Preheating of powders
 Walls and floor of the built cavity kept at the right temperature independently
 Top powder layer in the cavity heated just below the melting point of the polymer
 Use of IR heating modules and need to accurate T control
 Possibility of use of N2 atmosphere to prevent polymer oxidation

Convection channels in a powder bed (IR camera)

commercial Harvest Technologies machine
Bourell, Phys. Procedia 56 (2014) 147

9-zone heaters
in Integra machine

5
 1. SLS MACHINE TECHNOLOGY 6I

LASER ENERGY INPUT

Laser sources : Mainly CO2 also Nd:YAG (Kruth, Assembly Automation 23(2003)357)
Only a small fraction of additional energy is supplied by the laser beam

Energy density (ED) contribution of the laser beam :

PLS: Laser power (J/s)

VLS: Scan speed of the laser beam (mm/s)
DLS: Laser overlap (mm)
Bourell, Phys. Procedia 56 (2014) 147

6
 2. SLS POWDERS CHARACTERISTICS 7I

2.1 Production of relevant powders

 Emulsion/suspension polymerization spherical shape
well-controlled dimension and molar weight and unimodal distribution
 Precipitation from solution
Potato-shape particles
- Precipitation from hot-saturated or super-saturated solution
with good flowability
- Transfer of solution into a non-solvent
 (cryo) Milling and mechanical grinding Simple process but low yield
in the required size range,
irregular shape, risk of damaged particles
Commercial PA powders (Verbelen Eur Pol J 2016)

PA12 EOS 2200 EOS Orgasol Arkema PA11 Rilsan Arkema PA6 Sinterline Solvay
7
 2. SLS POWDERS CHARACTERISTICS 8I

 Coextrusion and dissolution

Technology transferred from the pharmaceutical sector
Extrusion of a blend of the desired polymer with a hydrosoluble polymer (PVA, PEG)
then removed by dissolution

Types of polymers : PA12,PBT, PP

Microstructure is controlled
by the composition and blend
processing conditions

Drummer, Proc. Eng.

102 (2015) 1918

Kleijnen, Applied Sciences

9 (2019) 1308

8
 2. SLS POWDERS CHARACTERISTICS 9I

2.2 Flowability criteria of powders

1st step: recoating of particles

Criteria from Drummer (Proc Eng 102 (2015) 1918) :
i) Sphericity at least 0.6 , ii) limited specific surface area ,
ii) iii) Control of particle size distribution, iv) no particle below 1 µm
v) D50 between 10 and 120 µm

Qualification of shapes (Schmid, Proc. PPS 34, Taipei, 2018)

Ccir, Ar, Ssol values close to 1 are preferred, another parameter defined: Elliptic smoothness

9
 2. SLS POWDERS CHARACTERISTICS 10I

HF = =
Other flowability criterion : Hausner ratio
1<HF<1.25
for commercial powders

Various flowability tests

are used

Powder
rheometer

Chatham, Prog. Pol. Sci. 93 (2019) 68

• Avalanche angle
From [Link], • Fluidization height
Hanser 2018 • Sedimentation time

Rotating drum
10
3. PROCESSING PARAMETERS AND POLYMER PROPERTIES 11I

Properties of polymers and powders regarding their use in SLS

11
3. PROCESSING PARAMETERS AND POLYMER PROPERTIES 12I

Polymers used in SLS :

• PA11 and 12 (around 90% of commercial applications)
• PE, UHMWPE, PP, TPU, TPE, PBT, PC, PAEK

Temperature profile of a standard SLS process and processing window

Drummer
Add. Manufact.
27 (2019) 379

The build chamber T must be higher than Tic and lower than Tim
 Model of Alscher: isothermal laser sintering is occurring
But only valid for the uppermost layers (case of PA12)
 The crystallization process is accelerated by super-cooling during powder re-coating
12
 3. PROCESSING PARAMETERS AND POLYMER PROPERTIES 13I

Stable Sintering Region (Vazquez, Proc Inst Mech Eng 225 (2011) 2240)

(1) processing window

(2)- SS Region
Melting without polymer degradation

Coalescence process of powders

0.5 Frenkel model
= of coalescence of powders
: surface tension, viscosity

Absorption of laser radiation

IR spectrum of PA12 with silica
Wavelength of CO2 laser is 10.6 µm M. Schmid
(943 cm-1) Hanser
Carbon black and silica are usually added 2018
(1wt% silica)
13
3. PROCESSING PARAMETERS AND POLYMER PROPERTIES 14I

Influence of Energy Density on mechanical properties and density of PA12

Caulfield, J Mat Proc Tech 182 (2007) 477
90° Building

0° Building

PA12 Duraform

14
3. PROCESSING PARAMETERS AND POLYMER PROPERTIES 15I

For short periods of storage near the melting points, post condensation dominates
over chain scission in N2 atmosphere (Drummer Phys. Proc. 56(2014)176)

Storage periods over 64 hrs lead to an decrease of molar weight due to chain scission

Ageing and recycling of powders (réf 178 chatham)

Powder ageing increase viscosity and molar weight

Some aged aggregates remain unmolten

15
3. PROCESSING PARAMETERS AND POLYMER PROPERTIES 16I

Influence of Laser Scan Speed on mechanical properties of PA12

A reduction of the melting depth for increasing exposure speed is supposed

Decrease of density and incomplete melting
Heat accumulation at the surface

Drexler, Phys . Procedia

Polymer degradation 78 (2015) 328
Sites of crack initiation 16
 4. SLS OF BLENDS AND FILLED PA12 17I

Sintering window for polymer blends in SLS

Limited possibility of common sintering window in semi-crystalline polymer blends

Mainly SLS blends with a minor component

PA12/PBT blends

PA6:PBT 90/10
PBT milled Precipitated Salmoria,
PA12 Opt. Laser. Tech.
PC/PBT blends 98 (2018) 92

The window processing of the

Greiner semi-crystalline polymer is located
Polym. Test.
beyond the Tg of the amorphous
64 (2017) 136
polymer

17
 4. SLS OF BLENDS AND FILLED PA12 18I

Incorporation of fillers in polymers through SLS technology:

 Physical blending of fillers and polymer powders

 (Cryo)milling of compounds of filled polymers obtained by twin-screw extrusion
 Coating of polymer powders by fillers using binding agents

Types of fillers in PA 12 : C-based

 Carbon black
Athreya, Mat Sci Eng A 527 (2010) 2637
 Graphite
Karevan, Carbon 64 (2013) 122
 Carbon nanotubes
Salmoria, Polym. Testing 30 (2011) 611 , Yuan, Polymers 8 (2016) 370
Yuan, Comp Part A 105 (2018) 203
 Carbon nanofibres
Goodridge, Polym. Testing 30 (2011) 94
 Carbon fibres
Chunze , Comp Sci Tech 71 (2011) 1834
Jing, Mater. Des. 116 (2017) 253
 4. SLS OF BLENDS AND FILLED PA12 19I

 Use of C- Based fillers is mainly aimed to improve mechanical properties

 Preparation of powders:
- Physical blending of pristine components is generally performed,
- Chemical modification of fibres to improve adhesion before blending
- Coating on polymer powder by the fibres
- Coating of fibres by precipitated polymer from solution before physical
blending with polymer powders
Salmoria, 2011
Physical blending

Yuan, 2016
Coating of CNT
on polymer
powders

Strong absorption of laser

radiation by MWCNT
 4. SLS OF BLENDS AND FILLED PA12 20I

Other types of fillers in PA 12

 Organomodified clays
Wang, Proc. IMecheE, 219 (2005) 11
Jain, Polym Composites 31 (2010) 732

 Silica
Chung, Mat. Sci. Eng. A 487 (2008) 251
Chunze, J. Reinf. Plast. And Comp. 28 (2009) 2889

 Calcium carbonate
Ippolito, Comp. Part B 164 (2019) 158

 Mo disulfur
Bai, J. Mat. Proc. Tech. 264 (2019) 382

 Aluminum
Mazzoli, Mater. Design 28 (2007) 993

 Glass beads
Cano, Eng. Fract. Mech. 203 (2018) 66
 4. SLS OF BLENDS AND FILLED PA12 21I

Formation of clay nanocomposites in situ through SLS processing

Octadecyl ammonium salt

in rectorite (OREC) (Wang 2005)

OREC

XRD spectra indicates intercalation

a) OREC, b) PA12-OREC 5%
Incorporation of organomodified montmorillonite (Cloisite 30B) entailed (Jain 2010) :
- Both aggregated and exfoliated fractions of C30B
- Incomplete melting of PA12,
- Reduction of some mechanical properties for 2wt% loading
PA 12 2%C30B

Young’s Mod. 737 809

(MPa)
Ultimate Tensile 49.2 48.4
Strength (MPa)
Elongation 36.9 14.6
at break (%)
 4. SLS OF BLENDS AND FILLED PA12 22I

Comparison of 2 nanosilica SLS PA12 processes (Chunze 2009) :

- Coated nanosilica with PA12 (via silane coupling in a solvent) blended with PA 12
powder (D-nanosilica)
- Raw silica blended with PA 12 powder (M-nanosilica)

3wt%silica
Coated
nanosilica
with
PA12

The use of coated silica

PA12 improves the mechanical
powder
properties but needs more
laser energy density
 5. FR PA12 SLS COMPOSITIONS 23

POLIFRIL PROJECT (IMT MINES ALES + SD TECH Company)

Supported by the region Occitanie (Readynov program – 18 months)

Previous works on FR polymers processed through SLS are very limited :

- Arai (Opt. Laser Tech. 117 (2019) 94)
FR PBT using a halogenated/Sb2O3 system, UL94V test and microcalorimetry
measurements but without interpretationof mechanisms
- Borille (Rapid Prot. J. 23 (2017) 169)
SLS processing and Mechanical test and of commercial FR PA12 in comparison
with virgin PA12

How to select FR systems devoted to SLS technology for PA12 ?

- Compatibility of components with laser irradiation instead of melt blending technology
(extrusion residence time at molten state and shearing),
- Limited number of components allowed,
- Influence of residual porosity on fire performance
(case of FDM : Regazzi et al, Pol. Deg. Stab. 2019)
- Fire performance of SLS compositions vs thermocompression ones

23
 5. FR PA12 SLS COMPOSITIONS 24

Different routes of incorporation of FR components in PA12:

- Direct blending of PA 12 and FR powders and fillers (dry blend)
- Extrusion of PA12+FR blends and micronization
- Aggregation of FR or fillers on PA12 powders using specific binders

Main issues of direct blending:

- Changes of the processing window in relation with crystallization processes
- FR powers/laser beam heat transfer and Energy density required
- Influence of FR powders on PA12 coalescence
Processing of square sheets (80 x 10 x 4 mm) for fire testing
EOS Formiga P110 Sharebot SNOWWHITE

24
 5. FR PA12 SLS COMPOSITIONS 25

 Few studies about flame retardant polyamides 11 and 12

 Most part of FR systems for PA devoted to PA 6 and PA 66
 PA11 and 12 decomposes without significant charred residue
and are sensitive to hydrolysis during melt processing

Limited performances of FR designed for PA6 due to the lack of charring

Risk of hydrolysis caused by hydrated mineral fillers acting by endothermal effect

Some systems tested:

Ammonium Polyphosphate (APP) Levchik, Pol. Deg. Stab. 36 (1992) 31

APP + Pentaerythritol + PP Liu, Pol Compos. 2009 30 (2009) 221
Intumescent system + CNT or nanoclays Lao, J Compos Mater 29 (2011) 479
Nanoboehmites Ferry, J Therm. Anal. Calorim 129 (2017) 1029

25
 5. FR PA12 SLS COMPOSITIONS 26

Various systems investigated in this study:

- Combinations of the FR alone and FR with submicronic particles (talc and kaolinite)
- Zinc borate used as promoter of vitreous structures able to reduce porosity during
fire testing
Sample PA2200 Exolit Exolit Aflammit Zinc Borate Kaolin Talc
AP422 OP950 PCO900

PA 100 0 0 0 0 0 0
AP30 70 30 0 0 0 0 0
OP30 70 0 30 0 0 0 0
AF30 70 0 0 30 0 0 0
ZB30 70 0 0 0 30 0 0
AP15ZB15 70 15 0 0 15 0 0
AP15OP15 70 15 15 0 0 0 0
AP10OP10ZB10 70 10 10 0 10 0 0
AP10AF10ZB10 70 10 0 10 10 0 0
AP10OP10ZB5KA5 70 10 10 0 5 5 0
AP10OP10ZB5TA5 70 10 10 0 5 0 5
• Exolit AP 422 : Ammonium PolyPhosphate (Clariant) • Zinc Borate : Firebrake ZB Rio Tinto
• Exolit OP 950* : Zinc diethylphosphinate (Clariant) • Talc : HAR T84 Imerys
• Aflammit PCO900* : Penterythritol ester of methane • Kaolinite : Paralux Imerys
phosphonic acid (Thor)
(*) FR action mainly in the gas phase 26
 5. FR PA12 SLS COMPOSITIONS 27

Sintering parameters :
Sample Chamber Laser Laser Scan Energy
Temperature Power (W) Speed Density
(°C) (mm/s) (J/mm2)
PA 142 4.2 2700 0.016
AP30 142 4.2 2700 0.016
OP30 142 4.9 2700 0.018
AF30 140 4.9 2700 0.018
ZB30 155 2.8 3600 0.008
AP15ZB15 153 2.8 3600 0.008
AP15OP15 142 2.8 2700 0.01
AP10OP10ZB10 152 2.8 3600 0.008
AP10AF10ZB10 150 2.8 3600 0.008
AP10OP10ZB5KA5 155 2.8 3840 0.007
AP10OP10ZB5TA5 155 2.8 3840 0.007

 The use of inorganic powders needs to increase the chamber temperature to avoid
warping phenomena (nucleating effects, thermal conductivity effects)
 Less laser energy is needed due to higher temperature for the chamber in the case of
mixed compositions with minerals
 « hot spots » caused by the inorganic particles able to absorb strongly the laser energy
could degrade locally PA12 also reduction of laser scan speed
27
 5. FR PA12 SLS COMPOSITIONS 28

Influence of FR on processing parameters

4 PA2200
15% OP950
15% M200 ΔT (°C)
Normalized Heat Flow (W/g)

3 15% MC50
15% Exolit AP422 PA2200 Aged 155-174°C
15% Aflammit PCO900
2 15% AP423
15wt% OP950 155-170°C
15wt% AP422 159-170°C
1
15wt% AP423 160-171°C
0 15wt% Melapur 200 157-170°C
15wt% MC50 162-170°C
-1
15wt% Aflammit 156-170°C
-2
DSC-PA2200 DRY BLEND
120 140 160 180 200
Température (°C)

AP422&AP423: Ammonium Polyphosphate (Clariant) Poor flowing

Melapur 200: Melamine Polyphosphate. Poor flowing
MC50: Melamine Cyanurate (BASF) Reduction of sintering window, poor flowing
 5. FR PA12 SLS COMPOSITIONS 29

PA2200+15% PA2200+15%
PA2200 MC50 Melapur 200 PA2200+5%Talc

Direct blending of submicronic fillers with PA12 powders is not adequate

 5. FR PA12 SLS COMPOSITIONS

30% AP422 30% ZnB 30% Aflammit 30% OP950

2,0mm 2,0mm 2,0mm 2,0mm

100 μm 100 μm 100 μm 200 μm

7% 8% 5% 14 %
 5. FR PA12 SLS COMPOSITIONS

Microstructure of specimens

All the specimens

are porous with
different open/close
porosity ratios.

Aflammit seems
particularly interesting
due to its ability to
soften at processing T

PA2200+10wt% PA2200+10wt% Low porosity

OP930 Aflammit
Measured density 1.05 Measured density 1.01
(pycnometer) (pycnometer)
Density calculated 0.90 Density calculated 0.98
from geometry from geometry
POWDER COALESCENCE: INFLUENCE OF FLAME RETARDANT

PA2200 Aged PA2200 Aged + 10% OP930

There is no interference of FR additives upon PA12 coalescence :

Case of an aluminium diethyl phosphinate
 5. FR PA12 SLS COMPOSITIONS 33

II.2 Evaluation of fire performance and discussion

Cone calorimeter (ISO 5660-1)

(35kW/m²)

Air flow control

 Time to Ignition (s)
 Heat Release Rate (kW/m²) = f(t) Hood
 Peak of Heat Release Rate (kW/m²)

 Total Heat Released (MJ/m²) Gas analysis

 Effective Heat of Combustion (kJ/g) Smoke opacity

measurement
Sample
 MARHE (Maximum of Average Rate
of Heat Emission (kW/m²) = f(t)
 Mass loss (%wt)= f(t)

 Smoke Opacity
Rate of Smoke Released = f(t)
33
 5. FR PA12 SLS COMPOSITIONS

Sample TTI pHRR EHC THR MARHE Résidu

(s) (kW/m2) (kJ/g) (MJ/m2) (kW/m2) (%)
PA2200 SLS 197 1580 34 151 422 -
PA2210 103 443 22 129 260 17
30AP SLS 83 632 31 135 321 19
30AP TC 76 475 31 103 295 20
30 OP SLS 142 783 24 138 350 1,2
30 OP TC 213 617 27,5 105 223 -
30 ZnB SLS 130 327 37 43,5 148 29
30 ZnB TC 101 330 38 135 205 30
30 Afla SLS 153 1224 37 145 376 2
30 Afla TC 123 871 27 115 295 6

SLS compositions present lower Time to Ignition and higher pHRR values
This is ascribed to :
- porosity of SLS samples,
- influence of laser on the formation of PA12 short chains
- possible degradation of FR due to irradiation (mainly OP 950, action in gaseous phase)
 35

SLS Thermocompression
PA2200
PA2210 1250
1600 30% AP422 PA2200
30% OP950 30% AP422
1400 30% Aflammit PCO900 30% OP950
1000
30% Zinc Borate 30% Aflammit PCO900
1200 30% Zinc Borate
HRR (kW/m²)

HRR (kW/m²)
1000 750

800

500
600

400
250
200

0
0
0 100 200 300 400 500 600 700 800
0 100 200 300 400 500 600 700 800 900
Time (s)
Time (s)
PA2200 100
100
PA2210
30% AP422
30% OP950 PA2200
80
80 30% Aflammit PCO900 30% AP422
30% Zinc Borate 30% OP950
30% Aflammit PCO900
Weight (%)

60 30% Zinc Borate

Weight (%)

60

40
40

20
20

0
0
0 100 200 300 400 500 600 700 800 900
0 100 200 300 400 500 600 700 800
Time (s)
Time (s)
 II SLS FLAME RETARDED PA 12
12,5% AP422+12,5% OP950+5% ZnB
600 12,5% AP422+12,5% Aflammit+5% ZnB
10% AP422+10% OP950+10% ZnB
10% AP422+10% Aflammit+10% ZnB

450
HRR (kW/m²)

300
Irr.
35kW/m2
150

0 10AP+10OP+10ZB 10AP+10AF+10ZB
0 150 300 450 600 750 900
Time (s)

Sample TTI pHRR EHC THR Residue Porosity

(s) (kW/m2) (kJ/g) (MJ/m2) (%) (%)

12,5%AP422+12,5%OP950+5 53 440 32 113 15 14

% ZnB
12,5%AP422+12,5%Aflammit 54 393 30 101 21 6
+5% ZnB
10%AP422+10%OP950+10% 81 431 33 145 22 13
ZnB
10%AP422+10%Aflammit+10 65 420 29 63 24 5
% ZnB
 II SLS FLAME RETARDED PA 12 37

30% AP422 30% ZnB 30% Aflammit 30% OP950

10% AP+10%OP+10%
15% AP+15% OP Height of intumescent
ZnB
structure : 45 mm

Combined FR modes of
action:
- Intumescent system
- Vitreous structure
- P radicals in gaseous
phase and dilution
 II SLS FLAME RETARDED PA 12

ANALYSE DES RÉSIDUS CÔNE CALORIMÈTRE

%P %Zn %C %Ti %Al %Si %B
PA2210 33 - 6,2 1,3 - 0,5 -
30% AP422 37 - nd 0,4 0,7 -
30% Zinc Borate 0,9 30 6,3 1 - - 19,5
10% AP + 10% ZnB + 10% 22,5 11,3 11,6 0,6 - - 8,2
Aflammit PCO900
15% AP +15% ZnB 21,3 15 8,3 0,9 - - 10,7

Taux de P
Borophosphate cristallisés synergistic effect publis

Aflammit PCO900
 II SLS FLAME RETARDED PA 12 39

ANALYSE DES RÉSIDUS CÔNE CALORIMÈTRE

10AP10OP10ZnB 10AP10AF10ZnB PA2210

30AP 30ZnB
 II SLS FLAME RETARDED PA 12 40

Kaolin/Talc CMC Coating of PA12 Pow

0,13% CMC Solution

 II SLS FLAME RETARDED PA 12

Coating of PA12 Powders

Échantillon TTI pHRR EHC THR MARHE Résidu
(s) (kW/m2) (kJ/g) (MJ/m2) (kW/m2) (%)
PA2200 SLS 197 1580 34 151 422 -
4% Kaolin enrobé SLS 137 1090 35 152 390 8,5
4% Kaolin enrobé TC 130 1100 37 160 412 5
4% Kaolin SLS 132 1060 27 113 335 8
4% Kaolin TC 140 1285 37 147 417 6
8% Kaolin enrobé SLS 145 673 n.d. 159 413 n.d.
12% Kaolin Enrobé SLS 124 665 37 185 345 9,8
4% Talc enrobé SLS 110 528 38 187 250 8
4% Talc enrobé TC 101 629 37 151 320 6
4% Talc SLS 172 1162 37 175 367 4,3
4% Talc TC 130 1050 37 153 375 4,1
8% Talc enrobé SLS 88 502 37 135 250 12
12% Talc Enrobé SLS 110 439 36 150 257 11
 II SLS FLAME RETARDED PA 12 42

Coating of PA12 Powders

1300

1200 1200
1100
PA/CMC + 4% Kaolin PA/CMC + 4% Kaolin
1000 PA + 4% Kaolin 1000 PA + 4% Kaolin
PA/CMC + 8% Kaolin 900 PA/CMC + 8% Kaolin
PA/CMC + 12% Kaolin PA/CMC + 12% Kaolin

HRR (kW/m²)
HRR (kW/m²)

800
800
700
600
600
500
400
400
300
200
200
100
0
0
0 250 500 750 1000 1250
0 100 200 300 400 500 600 700 800
Time (s)
Time (s)
 7. SLS OF PEBAX COPOLYMER 43

Few polymers for SLS process

New applications that needs materials with

specific mechanical behaviour

PEBAX® thermoplastic elastomers based on nylon

12 and poly(tetramethylene oxide)
 MEB DES PEBAX® BROYÉS

PEBAX® 2533

PEBAX® 5533

PEBAX® 7033
 SINTERING OF PEBAX® POWDERS

Échantillon T (°C) PLS Vb dLS ec Ed

PEBA2301 EOS 131 4,9 2700 0,1 0,1 0,16
PEBAX® 7033 135 4,2 2700 0,1 0,1-0,12 0,16
PEBAX® 5533 126 4,9 2700 0,1 0,12 0,15
PEBAX® 2533 78-84 4,9-9,1 2100-2700 0,1 0,12 0,15-0,36

ED=Energy Density(J/mm3) dLS

PLS=Laser Power (J/s)
𝑃 𝐿𝑆 VLS=Laser Scan Speed (mm/s)
𝐸𝐷=
𝑉 𝐿𝑆 𝑥 𝑑 𝐿𝑆 𝑥 𝑒 𝑐 dLS=Hatching distance (mm)
ec= Layer Thickness (mm)
 CARACTÉRISATION MÉCANIQUE PEBAX BROYÉS
25

20
Stress [MPa]

15
PEBAX SA-01 7033 Y
10
PEBAX SA-01 5533 Y

5 PEBA 2301 Y

0
0 100 200 300 400 500 600
Strain [%]

Reference E (GPa) ε (σmax) σrup ε (σmax) (%) σmax (Mpa)

(%) (Mpa)
PA2200 1,42±0,01 8±0,5 31,9±1,3 8,1±0,6 32,6±0,8
PEBAX 0,35±0,02 30,7±2,3 17,4±0,9 36,7±3,3 21,1±2,3
7033
PEBAX 0,18±0,01 500±34 19±0,7 507±35 21,1±0,7
5533
PEBA 2301 0,07 124±19 6±0,5 132±19 6,5±0,3
 CONCLUSIONS 47

 Specific features of 3D printed materials lead to a particular design

of flame retardant systems

 SLS processing of polymers with flame retardants leads to complex

issues related:
- to the selection of the relevant parameters,
(energy, temperature, laser power and speed…)
- to the laser/FR/polymer interactions.

 FFF technology allows to design core-skin and multilayer structures

in which FR components can be concentrated close to the surface
exposed to a radiant heat flux, leading to a saving of FR
components and optimization of other functional properties.
 5. FR PA12 SLS COMPOSITIONS

30% AP422 30% ZnB 30% Aflammit 30% OP950 PA2210

7% 8% 5% 14 %