AM-Materials and Processing

2/21/2024
Additive Manufacturing: Materials and Processing
Radha Raman Mishra, Ph. D.

Course Instructor
Assistant Professor of Mechanical Engineering
Need for appropriate materials

• Ability to produce the feedstock in a form amenable to the specific AM process
• Suitable processing of the material by AM
• Capability to be acceptably post-processed to enhance geometry and properties
such as –
 Microstructure
 Reduce porosity
 Finish surfaces
 Reduce roughness and
 Meet geometric tolerance
• Manifestation of necessary performance characteristics in service
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Materials used in AM
AM Materials
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Materials used in AM
Most frequently used materials: Polymers, Metals & Alloys, Ceramics and Composites
AM Processes Materials Remarks

Material extrusion Amorphous polymers Large viscous softening temperature range
Powder bed fusion • Semicrystalline A very small softening temperature range

• Metals & alloys with a dramatic change in viscosity
• Ceramics
Vat polymerization Photosensitive thermosets Mixing of ceramic particles possible
Material jetting Photosensitive thermoset Mixing of ceramic particles possible
Binder jetting Almost all in powder form Binder + Powder
Sheet lamination Almost all in sheet form Binder + Sheet
Directed energy deposition Metals & alloys, Ceramics Powder/wire form
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Polymers for AM
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Over view
Tan et al. (2020). Recent progress on polymer materials for additive manufacturing. Advanced Functional Materials, 30(43), 2003062. 7
Polymers
Polymerization: process of linking small molecules (monomers) into larger molecules

(polymers)
Polymer structures:
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Ian Gibson, David W. Rosen, Brent Stucker, Additive manufacturing technologies: rapid prototyping to direct digital manufacturing Springer, 2010.
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Polymers
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Thermoplastic polymers
• Soften or melt upon heating, and solidify upon cooling
• Allows to be remolded and recycled
Classification –
• Amorphous: (ex. polystyrene (PS) and polycarbonate (PC))
 Randomly ordered molecular structures that impart flexibility to the material
 Slowly soften and transform into a glassy state above Tg
 Do not have a defined Tm
• Semicrystalline: (ex. polyamides (PAs))
 Show both Tm and Tg that correspond to crystalline and amorphous regions,
respectively.
 Viscosity rapidly decreases as it changes from solid to viscous liquid phase
when heated above its Tm
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Dynamic DSC curve of a polymer and parameters

• Polymers are preheated to a bed
temperature (Tb) as close to Tm
(semicrystalline) and Tg (amorphous)
• Semicrystalline polymer, Tb <Tm,

onset (powder caking)
• Preheating serves to reduce the

temperature gradient between its
sintered and unsintered regions
• Mitigating the non-uniform

shrinkage of sintered parts
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Dynamic DSC curve of a polymer and parameters
https://doi.org/10.1016/j.cirp.2017.05.009 12
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Photopolymers
• Material that experiences a direct or indirect interaction with light to change its
physical or chemical properties.
• In contrast to the thermoplastic polymers, photopolymers have a cross-linked

molecular structure that do not melt and exhibit much less creep and stress relaxation.
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https://doi.org/10.3390/app11188545
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Photopolymer
• Mostly used by the VP and MJ • Form cross-linked chemical networks
• Liquid pre-polymers • Undergo irreversible hardening
• Activated upon irradiation
Converts the physical energy (incident light)

Photoinitiators into chemical energy (reactive intermediates)
Main constituent; reacts with photoinitiater

Liquid monomers to form polymer
Ensure safe processing and protect products

Photopolymer Stabilizers against aging and weathering.
Provides rigid plastic flexibility.to the polymer

Flexibilizers
Reactive diluents Added to adjust the viscosity of the mixtures

to an acceptable level
Ian Gibson, David W. Rosen, Brent Stucker, Additive manufacturing technologies: rapid prototyping to direct digital manufacturing Springer, 2010. 14
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Photopolymer Chemistry
UV radiation
Chemical Liquid
transformation Monomers
VP Resin Reactive Polymer
(Photoinitiators) Photoinitiators Chains
 Subsequently, cross-links forms (creation of strong covalent bonds between polymer chains)
 Types of photopolymer chemistry

o Free-radical photopolymerization—acrylate
o Cationic photopolymerization—epoxy and vinylether
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Photopolymer Chemistry
 Free-radical photopolymerization
o For every two photons (from the laser), one radical will be produced.
o That radical can easily lead to the polymerization of over 1,000 monomers
P–I: Photoinitiator
I●: a free radical
M: monomer.
 Termination of the polymerization

o Recombination (two polymer chains merge by joining two radicals)
o Disproportionation (cancelation of one radical by another, without joining)
o Occlusion (free radicals become “trapped” within a solidified polymer)
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Photopolymers
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Alim, M. D., Childress, K. K., Baugh, N. J., Martinez, A. M., Davenport, A., Fairbanks, B. D., ... & Bowman, C. N. (2020). A photopolymerizable thermoplastic with tunable mechanical performance. Materials Horizons, 7(3), 835-842.
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Key properties of photosensitive resign
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Key properties of thermoplastic powder
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Overview of polymer powders for SLS
Polyamideimide (PAI)
Polybutylene (PB-1)
Polyethersulfone (PES),
Polyimide (PI),
Poly(phenyl sulfone (PPSU),
Polysulfone (PSU),
Polytetrafluoroethylene (PTFE),
Poly(vinyl alcohol) (PVA),
Poly(vinyl chloride) (PVC),
Polyvinylidene fluoride (PVDF),
Styrene-acrylonitrile (SAN), and
Syndiotactic polystyrene (sPS)
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Key properties of a filament and their influences on FDM
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Overview of polymer filaments for FDM
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Ceramics for AM
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Ceramics
• Ceramics, due to their combination of high melting point and low toughness, are
difficult to process directly in AM
• In most cases, attempts to direct process ceramics have resulted in thermally

induced cracking
• Approaches to mitigate cracking include

 process optimization,
 adding auxiliary devices (ultrasonic, thermal, magnetic) and
 a doping toughening approach
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AM of Ceramics
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Ceramic AM Process
• L-PBF and
• DED
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Indirect AM
https://doi.org/10.1016/j.jmrt.2021.07.155
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Metallic Materials for AM
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Metals
• Common commercially available alloys are – pure titanium, Ti6Al4V, 316L stainless
steel, 17-4PH stainless steel and 18Ni300 maraging steel, AlSi10Mg, CoCrMo, and
nickel based superalloys - Inconel 718 and Inconel 625.
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AM processes for metals
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AM processes for metals
https://doi.org/10.1016/j.coche.2020.03.001
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Different phases of metals used in AM
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Multi-material System for AM
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Need of Multi-material systems

• Improving the mechanical properties of the resulting parts
• Providing additional functionality in the resulting part
• Improving the performance of the AM process
Vaezi, M et al. (2013). Multiple material additive manufacturing–Part 1: a review. Virtual and Physical Prototyping, 8(1), 19-50.
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Multi-material systems
• MM Systems include those produced from (Gibson et al. 2010) –
 Discrete multiple materials
 Composite materials and
 Porous materials suitable for secondary material infiltration
• However, the below cases do not fall in MM systems (Vaezi et al. 2013) as in these
processes the compositional variation cannot be freely controlled by computer and
program –
 Raw materials are pre-mixed or composited before the AM or
 Second materials is integrated by infiltration or coating or other non-AM post
processing methods
Vaezi, M et al. (2013). Multiple material additive manufacturing–Part 1: a review. Virtual and Physical Prototyping, 8(1), 19-50.
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Multi-material systems
(a) Different material systems: single-material, multi-material and FGAM prints

(b-c) nerve guidance conduit (d) MM chess parts
To achieve this, different materials or chemicals

need to be physically delivered to any spatial
location in 3D during the additive manufacturing.
Multi-material PLGA/collagen scaffold

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AM Processes for MM systems
Pei, E., Loh, G. H., Harrison, D., de Amorim Almeida, H., Verona, M. D. M., & Paz, R. (2017). A study of 4D printing and functionally graded additive manufacturing. Assembly Automation. 37
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AM vs conventional processes of MM systems –

• Enhance the performance of AM parts by adding more complexity and
functionality
• Possible to improve part performance by varying material compositions or type

within the layers
• Offers a whole new paradigm and range of opportunities for design, functionality,
and cost effective high value products.
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Composite materials
Definition:
• A material which is composed of two or more materials at a microscopic scale and
have chemically distinct phases
• Heterogeneous at a microscopic scale but statically homogeneous at macroscopic
scale
• Constituent materials have significantly different properties.
Classification of certain materials as a composite:

1. Combination of materials should result in significant property changes
2. Content of the constituents is generally more than 10%
3. In general, property of one constituent is much greater ( ≥ 5) than the other
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Composite materials
What are the constituents in a composite material?
• Reinforcement: discontinuous stronger harder
• Matrix: Continuous
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Functionally graded materials (FGM) systems

• Under the adverse atmospheric conditions (such as travel of a space plane in
atmosphere), failure occurs in conventional composite materials as they are unable to
meet the required performance criteria
• Naotake proposed a new class of

composite materials functionally
graded materials (FGMs)
• Based on the observations of

naturally grown materials and
structures, such as bone, wood,
teeth and fish scales etc.
Pei, E., Loh, G. H., Harrison, D., de Amorim Almeida, H., Verona, M. D. M., & Paz, R. (2017). A study of 4D printing and functionally graded additive manufacturing. Assembly Automation.
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• In contrast with conventional single-material and multi-material AM which focuses
on shape-centric prototyping, FGAM focuses on material-centric fabrication by
highlighting the structure-property relationship.
• FGMs are characterized by gradual transitions in either compositions/constituents

or microstructures (e.g., grain size, texture, porosity, etc.), along at least one
direction, leading to functional changes associated with at least one property
• FMG are two types, based on the various of properties properties –

 Continuous FMG
 Discontinuous FMG
Pei, E., Loh, G. H., Harrison, D., de Amorim Almeida, H., Verona, M. D. M., & Paz, R. (2017). A study of 4D printing and functionally graded additive manufacturing. Assembly Automation.
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(a) Discontinuous FGM
(b) continuous FGM
(c), (d) and (e) schematic

diagrams showing
discontinuous FGMs that
contain interfaces with gradual
change in composition, grain
orientation and volume
fractions of two types of
second-phase particles,
(f), (g) and (h) schematic

diagrams showing continuous
FGMs in absence of interfaces
and with gradual change in
grain size, fiber orientation and
volume fraction of second-
phase particles
Liu,et al. Functional gradients and heterogeneities in biological materials: design principles, functions, and bioinspired applications, Prog. Mater. Sci. 88 (2017) 467–498. 43
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FGAM
The potential microstructural gradient compositions achievable by FGAM can be
characterized into 3 types –
• Variable densification within a homogeneous composition
• Heterogeneous composition through simultaneously combining two or more

materials through a gradual transition; and
• Using a combination of variable densification within a heterogeneous

composition
Loh, G. H., Pei, E., Harrison, D., & Monzón, M. D. (2018). An overview of functionally graded additive manufacturing. Additive Manufacturing, 23, 34-44. 44
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Homogeneous compositions
Single-material FGAM
Varied densification
FGAM concrete by
Keating mimicking the
radial density gradient
of a palm tree
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Heterogeneous compositions
Multi-material FGAM
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Traditional vs FGAM composites
Thermal conductivity
Elastic modulus
Thermal Elastic
conductivity modulus
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Multi-material FGAM
Demonstrates a smooth and

seamless transition between
materials from 0% at one end to
100% to the other end in Multi-
material FGAM.
The continuous variation within

the 3D space can be achieved by
controlling the ratios in which two
or more materials that are mixed
during the deposition and before
curing.
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Multi-material FGAM
The design of heterogeneous
compositional gradients can be divided
into 4 types –
• A transition between 2 materials
• 3 materials or above
• Switched composition between

different locations, or
• A combination of density and

compositional gradation
Combination of density and compositional gradation within
a heterogeneous material.
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Shape Memory Materials
• SMA: shape memory alloy
• SMP: shape memory polymers
• SMH: Shape memory hybrids
• SMC: Shape memory composites
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Shape Memory Alloys
https://doi.org/10.3390/met11030415 51
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Shape Memory Polymers
Polymer network architectures suitable for

exhibiting a shape-memory effect (molecular
switches: red; net points: grey):
A) polymer networks consisting of switching
segments linked by covalent netpoints,
B) AB-polymer network
C) Polymer network having side chains as
switching segments
D) Multiphase polymer network consisting of
ABA triblock chain segments linked by
https://doi.org/10.1533/9780857097026.1.204 & https://doi.org/10.1002/adma.200904447 covalent netpoints. 52
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Shape Memory Hydrogels

• Hydrogels are three-dimensional network structures able to imbibe large amounts of water.
• Hydrogels do not typically dissolve due to chemical or physical cross-links and/or chain entanglements.
• They exist naturally in the form of polymer networks such as collagen or gelatin, can be made
synthetically.
10.1016/j.addr.2012.06.004 53
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Shape Memory Composites and Hybrid
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Shape Memory Composites and Hybrid
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Thank you
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AM-Materials and Processing

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AM-Materials and Processing

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2/21/2024

Additive Manufacturing: Materials and Processing

Radha Raman Mishra, Ph. D.

Need for appropriate materials

AM Processes Materials Remarks

Powder bed fusion • Semicrystalline A very small softening temperature range

Polymerization: process of linking small molecules (monomers) into larger molecules

• Allows to be remolded and recycled

Dynamic DSC curve of a polymer and parameters

• Semicrystalline polymer, Tb <Tm,

• Preheating serves to reduce the

• Mitigating the non-uniform

Dynamic DSC curve of a polymer and parameters

• In contrast to the thermoplastic polymers, photopolymers have a cross-linked

Converts the physical energy (incident light)

Main constituent; reacts with photoinitiater

Ensure safe processing and protect products

Provides rigid plastic flexibility.to the polymer

Reactive diluents Added to adjust the viscosity of the mixtures

 Types of photopolymer chemistry

 Termination of the polymerization

Key properties of photosensitive resign

Key properties of thermoplastic powder

Overview of polymer powders for SLS

Key properties of a filament and their influences on FDM

Overview of polymer filaments for FDM

• In most cases, attempts to direct process ceramics have resulted in thermally

• Approaches to mitigate cracking include

Metallic Materials for AM

AM processes for metals

AM processes for metals

Different phases of metals used in AM

Multi-material System for AM

Need of Multi-material systems

• Providing additional functionality in the resulting part

• Improving the performance of the AM process

(a) Different material systems: single-material, multi-material and FGAM prints

To achieve this, different materials or chemicals

Multi-material PLGA/collagen scaffold

AM Processes for MM systems

AM vs conventional processes of MM systems –

• Possible to improve part performance by varying material compositions or type

Classification of certain materials as a composite:

Functionally graded materials (FGM) systems

• Naotake proposed a new class of

• Based on the observations of

Functionally graded materials (FGM) systems

• FGMs are characterized by gradual transitions in either compositions/constituents

• FMG are two types, based on the various of properties properties –

Functionally graded materials (FGM) systems

(b) continuous FGM

(c), (d) and (e) schematic

(f), (g) and (h) schematic

• Variable densification within a homogeneous composition

• Heterogeneous composition through simultaneously combining two or more

• Using a combination of variable densification within a heterogeneous

Traditional vs FGAM composites

Demonstrates a smooth and

The continuous variation within

• A transition between 2 materials

• Switched composition between

• A combination of density and

Shape Memory Materials

• SMA: shape memory alloy