Tecnologie di manifattura additiva

Additive Manufacturing: quali materiali?

Dr. Marialaura Tocci

marialaura.tocci@unibs.it

AA. 2021/2022
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 Materiali per PBF

Principali leghe metalliche utilizzare per i processi Powder Bed Fusion

o Leghe di Titanio
o Superleghe base Nickel (Inconel, Hastelloy)
o Acciaio e acciaio inox
o Leghe di Alluminio
o Leghe Cobalto-Cromo
o Leghe di Rame
o Oro/platino
o Compositi/Oxide Dispersion Strengthened alloys (ODS)

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 Materiali per PBF
Leghe base Ti
Lavorazioni meccaniche difficili e costose → Vantaggio nell’utilizzare AM
➢ Ti commercialmente puro:
Grado 1 e 2, sono disponibili come polveri grezze.
Grado 2 è più resistente rispetto al grado 1, anche se la resistenza a corrosione
è comparabile.
Ti Grado 2 ha numerose applicazioni nell’industria medica perché è
estremamente biocompatibile.

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 Materiali per PBF
Microstruttura Ti grado 2

Titanium Grade 2 parts manufactured in the EBM process have a

microstructure consisting of fine α-grains, thanks to the rapid
cooling of the melt pool. The build chamber is kept at an elevated
temperature throughout the entire build, and the material thus
comes out of the EBM process in a naturally aged condition

https://additivemanufacturingllc.com/wp-content/uploads/2015/04/Titanium-Grade-2.pdf

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 Materiali per PBF
➢ Lega Ti6Al4V (Grado 5)
presenta resistenza e resilienza eccellenti, oltre a resistenza a
corrosione, basso peso specifico e biocompatibilità
→ Lega di Ti più utilizzata per Powder Bed Fusion (sia Laser che Electron
Beam)

(a) Directed energy deposited Ti6Al4V produces acicular α′

martensite phase.
(b) Selective laser melted Ti6Al4V microstructures also reveals α′
martensite.
(c) Electron beam melted Ti6Al4V has a fine α + β dual phase.
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 Materiali per PBF
Leghe base Ti
➢ Altre leghe di Ti di interesse per AM:
• Ti-24Nb-4Zr-8Sn → per applicazioni biomedicali (no elementi tossici e basso
modulo elastico)
• Ti-6Al-7Nb → per applicazioni biomedicali
• Ti-6.5Al-3.5Mo-1.5Zr-0.3Si → per il settore aerospace.
• γ-TiAl alloy (Ti-48Al-2Nb-2C) → aerospace (turbine blades…)

Ti-24Nb-4Zr-8Sn γ-TiAl alloy

Acetabular cup
https://doi.org/10.1002/adem.201500419

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 Materiali per PBF
Superleghe base Ni
Usate principalmente per applicazioni ad alta temperatura:
- Inconel 625 fino a circa 815°C;
- Inconel 713 elevate resistenza alla fatica termica (jet engine gas turbine
blades)
- Inconel 718, Superlega base Ni-Fe con altissima resistenza a corrosione
- Inconel 738, Eccellente resistenza a creep ad alta temperature e
resistenza a corrosion a caldo
- Hastelloy X Elevata resistenza meccanica e all’ossidazione a elevate
temperature; applicazioni fino a 1200 °C

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 Materiali per PBF

Directional columns of gamma (Ni3Nb)

precipitates in E-PBF fabricated Inconel 625
superalloy.
The arrow at lower right indicates the build (z-axis)
direction. The sample was over-etched to Vertical section views of melt pools and layer
exaggerate the columnar architecture striations in Inconel 718 fabricated by L-PBF

https://link.springer.com/content/pdf/10.1007/s13632-018-0433-6.pdf
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 Materiali per PBF
Leghe a memoria di forma Ni-Ti

Nitinol, a shape memory alloy of titanium and

nickel, is the material of choice for arterial stents
that need to return to their designed shape after
movement. Researchers have now shown that it is
possible to 3D print this alloy via powder bed https://www.additivemanufacturing.m
edia/articles/3d-printed-nitinol-opens-
fusion. new-possibilities-for-arterial-stents

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 Materiali per PBF
Acciaio
Principali acciai per AM:
➢ Acciai inox austenitici (AISI 316L e AISI 304L),
➢ Maraging steel (18Ni-300),
➢ Precipitation hardenable stainless steels (17-4 PH and 15-5 PH),
➢ Acciai da utensili (H11 and H13).

• Le alte temperature durante il processo

AM offrono la possibilità di formare
microstrutture peculiari.

• Bisogna considerare che i costituenti

microstrutturali possono cambiare in
funzione della velocità di raffreddamento
(per esempio, martensite e austenite
residua per gli acciai PH) https://www.3dprintingmedia.network/3d-
printed-hydraulic-block-subassemblies/

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 Materiali per PBF
Acciaio

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 Materiali per PBF
Acciaio
Struttura gerarchica tipica dei processi PBF

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 Materiali per PBF
Leghe di Al
➢ Leghe più utilizzate: famiglia Al-Si(-Mg)
• AlSi12 (no trattamento termico),
• AlSi10Mg (trattabile termicamente),
• AlSi7Mg (trattabile termicamente).
Sono leghe convenzionali da fonderia (Al-Si)
+ si distinguono per intervallo di solidificazione
ridotto

➢ Per applicazioni che richiedono prestazioni elevate: AlMgScZr (Scalmalloy®).

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 Materiali per PBF
Leghe di Al
➢ Leghe da deformazione plastica:
• Leghe serie 7000 (Al-Zn-Mg)
• Leghe serie 2000 (Al-Cu)
Solitamente opportunamente modificate per evitare fenomeno di solidification
cracking

➢ «Heat-resistant alloys» contenenti, per esempio lega FeAl–8.5Fe–1.3V–1.7Si

➢ Al-Li (lightweight constructions)

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 Materiali per PBF

Leghe di alluminio – processi Leghe di alluminio – processi

convenzionali L-PBF

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 Materiali per PBF
Il numero di leghe di Al per AM è ancora limitato. Come mai?
o Al è facile da lavorare con processi tradizionali
Vantaggio economico è limitato, soprattutto per componenti che
richiedono elevata produttività
o Al ha un’elevata riflettività alle lunghezze d’onda tipiche del laser e elevata
conducibilità termica
o Leghe di Al non sono facilmente saldabili.
o Tuttavia, l’elevata conducibilità termica:
- Riduce stress termico => riduce il bisogno di strutture di supporto;
- Permette alte velocità di costruzione.
o La bassa viscosità dell’alluminio può rappresentare un altro ostacolo.
o Alcune leghe da trattamento termico (e.g. EN AW-7075) contengono
elementi con una certa volatilità (Zn) => creano turbolenza nelle melt pools
→ porosità.
In vuoto, elementi con tensione di vapore molto diversa
dall’alluminio tendono ad evaporare.

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 Materiali per PBF
Leghe base Cobalto
Super leghe con elevate resistenza meccanica e a corrosione, non-
magnetiche e con buona biocompatibilità

➢ Co28Cr6Mo
• Comunemente utilizzata per protesi (articolazioni
artificiali, per esempio ginocchio e anca) per la
elevata resistenza a usura, la biocompatibilità e
l’assenza di Ni nella composizione chimica.
• Anche applicazioni strutturali (wind turbines)
• Gioielleria
Annealed and polished femoral (knee) prototype
built with porous mesh features for bone tissue
ingrowth at femoral attachment shown in
corresponding views.
https://link.springer.com/content/pdf/10.1007%2Fs11661-010-0388-y.pdf
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 Materiali per PBF
Leghe base Cobalto
➢ Co28Cr6Mo

Micrografie ottiche della lega Co28Cr6Mo processata con L-PBF

allo stato non trattato: evidenza dei diversi elementi che
costituiscono la microstruttura gerarchica

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 Materiali per PBF
Leghe di Cu
Alta conducibilità termica + alta riflettività ottica → dissipa velocemente
calore ed energia → serve laser con elevata potenza
➢ CuSn10 ha proprietà termiche ed elettriche eccellenti
 micro-heat exchangers, con pareti sottili e geometrie complesse.
➢ Cu-Cr-Zr: lega trattabile termicamente con elevata durezza e
conducibilità termica

Different components made of CuCrZr alloy produced by SLM.

(a) Microchannel device with connection ports,
(b) lattice structure (filter) with 500 µm in beam diameter
(c) housing for high-power laser device with integrated cooling components for electronic
packaging.

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 Materiali per PBF
Leghe di Cu
Alta conducibilità termica + alta riflettività ottica → dissipa velocemente
calore ed energia → serve laser con elevata potenza
➢ CuSn10 ha proprietà termiche ed elettriche eccellenti
 micro-heat exchangers, con pareti sottili e geometrie complesse.
➢ Cu-Cr-Zr: lega trattabile termicamente con elevata durezza e
conducibilità termica

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 Materiali per PBF
Metalli refrattari
Leghe e metalli puri alto fondenti, elevata resistenza ad
alta temperatura, schermatura da radiazioni
• Tungsteno,
• Tantalio,
• Niobio,
• Molibdeno

Leghe di Magnesio
AZ60, AZ91…
Per applicazioni biomedicali (leghe biodegradabili)

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 Materiali per PBF
Oxide dispersion strengthening (ODS) alloys
Oxide Dispersion Strengthening (ODS) alloys → addition of stable oxide
nanoinclusions in the alloy matrix by mechanical alloying or pre-alloying
Mainly for steels and Ni-based alloys → to improve mechanical properties
at high temperature

Limitations
- the agglomeration/segregation of
nanoinclusions
- the formation of defects, i.e.,
cracks and voids, and the
coarsening of nanoinclusions
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 AM: Quali materiali?
➢ Multi-materials / Functionally Graded materials

https://doi.org/10.1016/j.matdes.2017.05.034

Source: Centre for Additive Manufacturing (CfAM)

University of Nottingham

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Alloys design

24
 Alloys for AM

➢ Nowadays, only a limited number of alloys are successfully process-

able by additive manufacturing
➢ Optimization of alloy compositions to develop materials tailored for
these processes is still limited
→ The main approach is to simply use conventional alloys, developed for
traditional manufacturing processes → this is a serious limitation → alloys
are not designed to exploit the potential of AM technologies

On the other hand, not all the materials are suitable for their application in AM

→ first, it is necessary to identify the main features of the process, defects

formation as a function of material composition and process parameters

→ based on this, it is possible to identify general rules for new alloys design

Analogy with laser welding!

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 Tools for alloys design
Numerical/theoretical approach

1. Thermodynamic models → calculation of formation of phases after

solidification as a function of chemical composition, temperature and
pressure (ex. CALPHAD method) → phase diagrams, equilibrium
condition

2. Kinetic models → take into account the kinetics of solidification

phenomena → the higher the solidification rate, the higher the difference
between the final real structure and the microstructure in equilibrium
condition

Limits
• Alloy composition can be very complex (many alloying elements) →
calculations to consider many alloying elements take a long time
(evaluation of all the possible combinations…)
• Based on database of material properties and their reliability
• Strong dependence of material properties on kinetics of the process →
many parameters to consider

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 Tools for alloys design

Experimental approach
Tests carried out on a discrete number of alloys with different composition
and recording of data from experimental characterization

Limits
• Time and material consuming
• Difficult and expensive to produce small batch of metal powder by means
of atomization processes
• It is necessary to acquire a significant amount of data → difficult if
characterization techniques are not automated
• Trial-and-error approach

Combination of numerical and experimental approach

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 Tools for alloys design

AM processes are characterized by manufacturing a small quantity of material

with:
➢ High temperature of molten material and high melting rates

• Evaporation of volatile elements → element loss

• Turbulent flow in the melt pool → porosities

➢ High solidification and cooling rate

➢ High thermal gradient Gravity Casting
Cooling rates ~ 10 - 102 K/s
• Non-equilibrium solidification
• suppressed phase transformations,
• supersaturated phases → “self- Powder bed fusion
quenching”, Cooling rates ~ 105 – 106 K/s
• segregation,
• thermal residual stresses,
• hot cracking.

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 AM: Quali materiali?

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 Hot cracking

Many alloys cannot be processed because of cracking

→ this is not dependent on optimization of process parameters but only to
the properties of the alloy

Different type of cracks can generate due to different metallurgical origins:

• Solidification/liquation cracking.

Parameters affecting formation of solidification cracking:

• Solidification Temperature Range
• Amount and Distribution of Liquid during Terminal Stage of Solidification

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 Hot cracking

Parameters affecting formation of solidification cracking:

• Solidification Temperature Range
→ A wide solidification interval promotes cracking
• Amount and Distribution of Liquid during Terminal Stage of Solidification
→ Solidification of low melting phases that segregates at grain boundaries
leads to cracks formations (+ phases with different thermal expansion
coefficient)

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 Processability of 7075 Al alloy
Alloys belonging to the 7xxx series are suitable for many applications in
aerospace industries as they are characterized by high specific strength
and toughness achieved mainly through the precipitation of the
MgZn2 phase. However, these alloys are not weldable because they suffer
strongly from liquation cracking.

Al7075, with a high content of Zn, Mg and Cu combines high strength and
high toughness → used in automotive, aerospace, aviation or construction
industries.

Several trials to process 7075 Al alloy → Many problems:

- Quantity of zinc evaporates as a consequence of the extremely high

temperatures of the melt pool → reduction in the zinc content in the
chemical composition of the final part
- Formation of cracks, all oriented along the grain boundaries (coarse
columnar grains), form during the L-PBF process of this alloy

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 Processability of 7075 Al alloy

Cracking phenomenon
due to the presence of a thin liquid film at the grain boundaries that cannot
follow the shrinkage due the solidification.

in L-PBF samples, cracks are oriented along the building direction

→ the cracks that generate during the laser scanning are oriented along
the building direction as they follow the columnar grain boundaries

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 Processability of 7075 Al alloy

How to reduce this cracking phenomenon?

• a narrow solidification range,

• a high fluidity of the molten phase,
• a low coefficient of thermal expansion (CTE)
• a reduced solidification shrinkage

→ Addition of Silicon → creation of a new alloy

Silicon decreases the melting temperature and solidification range (through

the formation of a eutectic mixture), while improving the fluidity and
reduces the thermal expansion
→ confirmed by thermodynamic simulation

the large solidification range with a low solidus temperature leads to

sensitivity to hot cracking….

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 Processability of 7075 Al alloy

First tests → mixing powders of Al7075 alloy and pure Si

+ verification that it is possible to obtain samples with a homogenous

composition starting from mixed powders.

https://doi.org/10.1016/j.jmatprotec.2016.08.003

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 Processability of 7075 Al alloy

https://doi.org/10.1016/j.jmatprotec.2016.08.003

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 Processability of 7075 Al alloy
Cracks follow grain boundaries between coarse columnar grains
→ very fine grained zones + reduction in grain size → hinder crack
formation and growth.

Al7075 alloy Al7075 alloy + 4% Si

large, vertically oriented grains fine grains increase the total
and grain boundaries → grain boundary surface area
provide an easy crack growth within a given volume → avoid
path. intergranular cracking
(Cracks that do form are stopped quickly,
because the crack continuously needs to branch
https://doi.org/10.1016/j.jmatprotec.2016.08.003 along a new grain boundary surface)
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 Processability of 7075 Al alloy
Formation of more eutectic formation of more low melting point
phase that solidifies at eutectic that could backfill the cracks
lower temperatures during the last stage of solidification

Al7075 alloy

Al7075 alloy + 2% Si

Al7075 alloy + 4% Si

DSC thermograms Decrease of melting point

https://doi.org/10.1016/j.jmatprotec.2016.08.003
Lower melting temperature → narrow solidification
range → helps the processability of the material
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 Processability of 7075 Al alloy
7075 alloy 7075 alloy + AlSi10Mg

Si addition

Liquation cracking
• Lower viscosity
• Reduced solidification
presence of a thin liquid temperature range
film at the grain boundaries • Reduced thermal expansion
that cannot follow the coefficient
shrinkage due the
solidification No cracks

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 Alloys for AM

Other aspects related to powder production:

• Loss of volatile elements during atomization
• Formation of unexpected phases during solidification in the
atomization chamber → the process is complex and often the final
composition of the powder is different from that of the precursor
material
• It is expensive to produce small batches of powder with innovative or
ad-hoc compositions → effort in developing small-scale atomization
plants

• Difficult to obtain the raw feed material for powder production in the
required condition (for instance as bars for EIGA process)

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 Alloys for AM

In-situ alloying → mixing pure metals powders with alloy powders

Promising route to produce novel alloy compositions with increased

process-ability

mixing with elements that would enhance the absorptivity,

surface tension, viscosity and other properties of the alloys

To increase alloys for AM applications

Possibility to produce small batches of powders with non

commercial composition to develop new alloys for AM

One of the challenges in designing alloys this way is understanding how

different the materials respond to laser irradiation during processing –
individually and combined with others – as this is essential to enable the
prediction of the properties and behavior of the resultant material

Main problem → formation of segregation in the component

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Leghe per Binder Jetting

42
 Materiali per Binder Jetting
Vantaggi del Binder Jetting

• Non avviene fusione delle polveri → meno limitazioni dal punto di vista
della formazione di solidification cracks…
→ Potenziale di applicazione per una più ampia gamma di materiali

• Processo avviene a temperatura ambiente e atmosfera non controllata

→ No problemi legati a ossidazione, stress residui, segregazioni,
cambiamenti di fase
→ Camera di costruzione di dimensioni maggiori rispetto a PBF
(2200x1200x600 mm)

• No necessità di supporti

• Elevata produttività

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 Materiali per Binder Jetting

• Super leghe base Ni

o In718
o In625
• Magnetic materials
o Ni-Mn-Ga
o Fe-6Si
• Titanio commercialmente puro Co-Cr-Mo

• Rame puro
• Acciai
o AISI 316
• Leghe base cobalto
o Co-Cr28-Mo6

binder jetted alloy 625.

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 Materiali per Binder Jetting
➢ Binder jetting di Ti commercialmente puro

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 Materiali per Binder Jetting
➢ Binder jetting di Fe puro

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