University of Tennessee, Knoxville

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University of Tennessee Honors Thesis Projects University of Tennessee Honors Program

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Improving and Understanding Inter-filament

Bonding in 3D-printed Polymers
Madeline S. Stark
University of Tennessee, Knoxville, [email protected]

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 Improving and Understanding Inter-filament Bonding in 3D-printed Polymers

A Thesis Submitted to the Faculty

Of The University of Tennessee

by Madeline S. Stark

May 2016
Department of Chemistry, The University of Tennessee, Knoxville TN
Honors Thesis, The University of Tennessee, Chancellor’s Honors Program

Thesis Defense Committee:

Dr. Mark Dadmun, Advisor

Dr. Brett Compton

Dr. Bin Zhao

1
TABLE OF CONTENTS
List of Tables and Figures……………………………………………………………………...3
Abstract…………………………………………………………………………………………..4
Chapter 1: Introduction ………………………………………………………………………...5
Chapter 2: Materials and Methods.………………………………………………………….10
2.1: Interfacial Adhesion Measurements……………………………………………………10
2.2: Thermal thiol-ene polymerization modification………………………………………..12
Chapter 3: Results and Discussion………………………………………………………….13
Chapter 4: Conclusion………………………………………………………………………...21
References……………………………………………………………………………………..22
Appendix: 1H-NMR spectrum of non-modified ABS……………………………………….25

2
List of Tables and Figures
Table 1. Measured temperature of the top layer of the bottom half of the T-peel samples
after pause times

Table 2. Comparison of the percent composition of the cysteamine and DODT-modified

ABS with non-modified ABS

Figure 1. Thiol radical addition proceeding in an anti-Markovnikov fashion

Figure 2. Model of a representative T-peel sample

Figure 3. T-peel test on ORNL's Universal Testing Machine

Figure 4. Instron testing machine

Figure 5. Structures of cysteamine and 2,2'-(ethylenedioxy)diethanethiol

Figure 6. Interfacial adhesion data neat ABS, DADPM and CuSO4-treated samples

Figure 7. Interfacial adhesion data for the neat ABS and AIBN treated samples.

Figure 8. Targeted structures of cysteamine- and DODT-modified ABS

Figure 9. 1H-NMR spectrum of cysteamine-modified ABS

Figure 10. 1H-NMR spectrum for DODT-modified ABS

3
Improving and Understanding Inter-filament Bonding in 3D-printed Polymers

Abstract

This paper examines the inter-filament bonding within Fused Deposition

Modeling (FDM) 3D printed parts as well as the covalent modification of acrylonitrile-

butadiene-styrene (ABS) copolymer. A fundamental limitation of 3D printed parts is that

they are affected by anisotropy, which results in weak inter-filament bonding. Chemical

cross-linkers were applied to the interface of T-peel samples to increase the inter-

filament bonding of 3D printed parts in the z-direction. The interfacial adhesion between

adjacent layers was quantified using the T-peel test and inter-filament bonding was

improved with 4,4′-diaminodiphenylmethane (DADPM) as the chemical cross-linker.

Additionally, the post-polymerization modification of ABS was demonstrated

through a thiol-ene “click” reaction. The thiol-modified ABS was characterized using
1H-NMR spectroscopy. Percent composition of the modified ABS calculated from peak

integrations indicate that the thiol added to the polybutadiene segments. These studies

increase our understanding of chemically crosslinking layers in FDM to improve the

strength of 3D printed parts and provide pathways to covalent bond formation between

adjacent layers within the part. Further improvements to FDM technology will allow for

the creation of mechanically robust, geometrically complex parts that are useful in a

wide range of applications.

4
Chapter 1: Introduction

Additive manufacturing (AM), the production of 3D objects, has rapidly become a

method of creating prototypes for manufacturing. Unlike traditional manufacturing

techniques which utilize molds or welding, AM involves layer-by-layer synthesis of parts.

The layer-by-layer process allows for greater freedom of design and flexibility of shape

and part orientation in the manufacturing industry. With this rapid growth comes the

need to understand the technique as well as improve the methodology. A common AM

technique is Fused Deposition Modeling (FDM). In FDM, a 3D model is created in

AutoCAD and the STL file is sent to SlicR, a program that slices the model into thin

layers. These layers represent the 2D sections that, when stacked on top of each other,

emulate the 3D printed object1. Once the layers have been generated, the g-code is

sent to the 3D-printer. The polymer filament passes through the heating element, which

is heated to a temperature just below the melting point of the polymer1. Upon passing

through the heating element the filament becomes semi-molten, goes through the

extrusion nozzle and is then deposited layer-by-layer on a glass bed platform. During

the printing process, the printer head moves in the X-Y plane according to the geometry

specified by the software while the platform adjusts in the Z-direction so that new layers

can be deposited.

Thermoplastic polymers are ideal filaments for FDM applications since they

soften above a certain temperature and solidify below that temperature2. Above the

critical temperature, a thermoplastic can be molded or extruded and then cooled.

However, many thermoplastic polymers such as polystyrene are rigid and brittle, which

limits their applications in manufacturing, where toughness is critical to creating quality

5
parts. To increase the toughness of brittle polymers, an elastomer is added to form a

copolymer with two phases. Acrylonitrile-butadiene-styrene (ABS) is one such

copolymer. In this polymer, dispersed butadiene particles make up the rubbery phase

and contribute to toughness, while poly(styrene-co-acrylonitrile) (SAN) is responsible for

the formability of the polymer3. Since the butadiene particles have layers of SAN grafted

onto their surfaces, the two phases are capable of interacting, creating a polymer that is

both tough and moldable3. ABS is a common material for traditional manufacturing

techniques, particularly injection molding, due to its toughness and moldability4.

Currently, it is used in the production of car parts, household appliances, medical

devices, and a variety of other applications2. Because of its importance in the plastics

industry, ABS is one of the target thermoplastics for FDM applications.

The next step in the growth of additive manufacturing is transitioning from

prototyping parts to manufacturing them using FDM or similar techniques. However, the

leading drawback to replacing traditional manufacturing techniques with FDM is that 3D-

printed parts lack the toughness, impact strength and consistency of manufactured

parts5. This lack of quality is mainly due to anisotropy, the property of being directionally

dependent, which affects 3D-printed parts. In FDM, filament is laid down layer-by-layer

in a crisscross manner and once the molten filament is extruded, the heat dissipates

rapidly. By the time the next layer is deposited, the first layer has cooled and therefore

diffusion between the two layers is limited. Perpendicular to the printed layers, the

interlayer adhesion is particularly weak, limiting toughness and robustness 6. Since the

3D-printed part’s properties are not identical in all directions, studies have found that

anisotropy can reduce the impact strength by as much as 90%7 and the tensile strength

6
by as much as 85 %8. Thus, reducing anisotropy is one of the foremost challenges in

transitioning FDM technology from prototyping to manufacturing parts. Previous studies

have attempted to understand and mechanically reduce anisotropy in 3D-printed parts

by changing print orientation, or the printing path6–8. Other research has chemically

modified the copolymer, incorporating carbon nanofibers9 or glass fiber into the ABS

filament10. Although these methods have resulted in parts with greater stiffness and

strength, printed part flexibility and handleability are significantly reduced.

Chemical crosslinking is another method of improving adhesion between

adjacent layers. Crosslinking involves the formation of either noncovalent or covalent

bonds between polymer chains. A variety of experiments have investigated the

formation of noncovalent bonds in polymer systems, including ionic crosslinks in

carboxylated-nitrile rubber (XNBR)11 and hydrogen bonding in the supramolecular

network of maleated polyethylene-octene elastomer12. In the aforementioned cases, the

noncovalent crosslinking resulted in improved mechanical properties for the tested

polymer systems. It is unlikely, however, that noncovalent crosslinking would be

amenable to FDM applications since noncovalent interactions are not as resistant to the

higher temperatures required by FDM as covalent bonds. For example, covalent

crosslinking of epoxy resins utilizing diamines as chemical hardeners has resulted in

materials with greater tensile strength but these materials have not been sufficiently

studied for FDM applications13. Additionally, ionizing gamma radiation has been shown

to effectively increase the chemical resistance while reducing anisotropy in 3D-printed

shape memory polymers when used as a crosslinking agent14. Consistent exposure to

penetrating gamma rays, however, poses a health risk to the operator and can cause

7
cellular damage. Therefore, a more user-friendly crosslinking technique that promotes

the formation of covalent bonds is needed.

The question of crosslinking centers on whether or not covalent bonds can form

between polymer chains of adjacent layers in FDM. For this to occur, the ABS filament

must be amenable to post-polymerization modification. Post-polymerization modification

is a powerful tool for creating functional materials since it involves the direct reaction of

functional groups that are inert to polymerization conditions but can readily convert into

a broad range of other functional groups. This method is convenient for functionalizing

polymeric-active esters with amine groups as well as activated alkenes with thiols

through a Michael Addition reaction in mild conditions15. Although not a novel method of

modifying polymers, radical thiol addition has also been investigated recently to

functionalize polymeric alkenes, such as 1,2-polybutadiene16. In the presence of UV-

light or a radical source, thiols add to the least substituted carbon of the double bond

(Figure 1).

Figure 1: Thiol radical addition proceeds in an anti-Markovnikov fashion15.

Such “click reactions” have several benefits, namely that they have high yields, good

specificity and minimal byproducts. Current research has utilized the thiol-ene click
8
reaction to create cross-linked polymeric matrices for synthetic, degradable hydrogels17,

dental restorative materials18 as well thermo-sensitive electrospun fibers19. Although

Campos and Hawker describe the thermal and photochemical thiol-ene click reactions

for a diverse array of polymer systems20, to date, ABS has not been characterized using

these methods. Since the butadiene component of ABS contains a double bond capable

of reacting with the thiol under a UV or radical source, it is a potential substrate for the

thiol-ene click reaction. Consequently, demonstrating that post-polymerization

modification is a viable option for ABS would provide a pathway to form covalent bonds

between the adjacent layers of ABS filament during the print process.

Therefore, this experimental research program seeks to address the efficacy of

chemical cross-linking to improve the quality of inter-filament bonding as well as to

demonstrate the post-polymerization modification of ABS to create filament that can

readily undergo post-deposition cross-linking reactions between layers.

9
Chapter 2: Materials and Methods

2.1 Interfacial adhesion measurements

To determine the interfacial adhesion between layers of the 3D printed parts, six

T-peel samples were printed for each sample set (Figure 2).

Figure 2: Model of a representative T-peel sample.

For the first three sample sets, the bottom portions of the samples were printed and the

printing was then paused for either 0, 30 or 60 minutes. The purpose of the pause times

was to determine the effect of cooling of the layer on the strength of adhesion between

the layers. Before restarting the printer, the surface temperature of the printed part was

recorded with an IR-thermometer to quantify the amount of heat lost during the pause

time. The t-peel test was utilized to determine the strength of the interface.

For the second set of samples, the printer was once again paused for 0, 30 and

60 minutes. After each pause time, however, a layer of a chemical cross-linker was

painted onto the exposed surface of the bottom portion of the part before resuming

printing. The chemical cross-linkers utilized were 2,2-azobisisobutanitrile (AIBN), copper

(II) sulfate pentahydrate and 4,4′-diaminodiphenylmethane (DADPM). The cross-linkers

were selected to react with the functional groups of ABS. In CuSO4, the Cu2+ ions can

form coordination bonds with the acrylonitrile groups on contiguous layers. Alternatively,

AIBN decomposes into radicals that can react with the C-C double bond of butadiene

10
and initiate the formation of covalent bonds between adjacent layers. DADPM should

also react with the carboxyl groups resulting from the degradation of butadiene during

deposition. All three solutions were 10 % by weight in acetone. To prepare the copper

(II) sulfate solution, the blue copper sulfate hydrate was first heated to remove water

and form CuSO4 and was then suspended in acetone to create a 10 % by weight

solution. It is hoped that the addition of a chemical cross-linker will chemically bond

adjacent layers together and improve the strength of the interlayer adhesion. To

quantify the effect of adding the cross-linkers, the interfacial adhesion of the interface

was measured using the T-peel test.

The T-peel test was applied to the samples to determine the interfacial adhesion

between the two layers. The DADPM and CuSO4 experiments were performed on a

custom Universal Testing Machine (UTM) at Oak Ridge National Laboratory (Figure 3).

The load cell was 50 lbs. and the rate of testing was 0.069 in/min. The AIBN

experiments were performed on the Instron at the University of Tennessee’s Center for

Renewable Carbon, at a rate of 2.1 x 10-3 mm/s with a 100 lbs. load cell (Figure 4).

Figure 3: T-peel test on ORNL's UTM Figure 4: Instron testing machine

11
Once the force required to peel the samples was obtained, the interfacial adhesion (G a)
𝐹
was calculated using the equation: 𝐺𝑎 = 𝑊, where F is the force needed to separate the

layers in Newtons and W is the width of the sample in meters.

2.2 Thermal thiol-ene polymerization modification

To determine whether covalent bonds can form after polymerization, a series of

thiol-ene polymerization reactions using a procedure similar to that described by

Campos and Hawker were performed20. In these experiments, ABS polymer beads, 5-

10 equivalents (with respect to the alkene) of thiol, and 0.50 equivalent of AIBN were

added to an ampule. The thiols utilized in the experiments were

2,2-(ethylenedioxy)diethanethiol (DODT) and cysteamine (Figure 5).

Figure 5: Shows the structures of cysteamine (L) and 2,2'-(ethylenedioxy)diethanethiol (R).

A minimal amount of THF was added to solubilize all components. Next, the solution

mixtures were degassed using three freeze-pump-thaw cycles, and then heated at

80 oC for 2 hours. Once the reaction was complete, the modified polymers were purified

by precipitation into ethanol. The purified polymers were then characterized using 1H-

NMR spectroscopy at 300 MHz in CDCl3.

12
Chapter 3: Results and Discussion

Interfacial adhesion measurements

Figures 6 and 7 show the interfacial adhesion measurements using data from the

t-peel tests. The black squares on both figures represent the neat ABS, where no

chemical cross-linkers were applied. Samples treated with a CuSO4 solution are

represented by the blue triangles on Figure 6 while the red circles denote samples that

were treated with a solution of DADPM after a pause time. On Figure 7, the red

triangles show the data for the samples treated with a solution of AIBN. As pause time

increases, the data show a clear decreasing trend in interfacial adhesion among all

sample sets. This decreasing trend is due to the fact that when a layer is deposited, the

heat rapidly dissipates from the surface of the newly deposited layer. This heat loss

limits the intermolecular diffusion between the first layer and the next layer, decreasing

inter-filament bonding.

The blue triangles on Figure 6 show that samples treated with the CuSO4

solution did not demonstrate increased inter-filament bonding but rather a marked

decrease below that of the neat ABS samples. This indicates that adding a Cu 2+

suspension impedes rather than promotes interfacial adhesion. Although Cu 2+ can form

coordinating bonds with the nitrile, –CN, group at sufficiently high temperatures, the

decrease in interfacial adhesion over both sets of samples suggests that coordinating

13
bonds were not formed in this work.

Figure 6: Shows the interfacial adhesion data for the neat ABS, DADPM and CuSO4-treated samples.

One explanation for this phenomenon is that Cu2+ can also coordinate with

water molecules, possibly acquired from the water vapor in the environment or from the

acetone solution. The formation of strong coordination bonds with water prevents Cu 2+

ions from coordinating to the nitrile groups on the deposited ABS filament. However,

Cu2+ coordination to water molecules does not explain the marked decrease in inter-

filament bond strength compared to the neat ABS samples. Restructuring on a

molecular level could have occurred during the painting of the surface with the acetone

solution reducing inter-filament bonding below that of the neat ABS, however, this

phenomenon is not well-understood in the context of this research.

14
 Figure 7: Shows the Interfacial adhesion data for the neat ABS and AIBN treated samples.

Figure 7 presents the surface adhesion data for neat ABS as well as ABS

samples treated with AIBN initiator. The neat samples demonstrate the same downward

trend in interfacial adhesion with increased pause times as discussed above. The figure

also shows that the application of AIBN solution to the deposited layers resulted in a

decrease in interfacial adhesion, indicating that the AIBN initiator solution, like the Cu 2+

suspension, inhibits inter-filament bonding. A thermal initiator, AIBN decomposes above

65 oC to form two 2-cyanoprop-2-yl radicals. These radicals can initiate crosslinking

between butadiene monomers within the ABS layers. The data suggest that this cross-

linking did not occur since the interfacial adhesion decreased from that of neat ABS for

samples with both 30 minute and 1 hour pause times. Even though the samples were

printed at 210oC with a bed temperature of 100oC, the temperature of the top layer of
15
the bottom half of the printed t-peel part was found to be 52oC at a pause time of 0

minutes which suggests that the samples do not remain at temperatures high enough to

decompose AIBN (Table 1).

Pause Time Temperature After Pause Time

(minutes) (°C)
0 52
30 46.8
60 33
Table 1: Shows the temperature of the top layer of the bottom half of the t-peel part after pause times.

Since the pause times for both sample sets were 30 or 60 minutes, the temperature of

the samples had dropped well below 65 oC before the addition of AIBN. Also, as seen in

the CuSO4 samples, acetone evaporation could have further decreased the temperature

of the layers. Both factors would result in a decrease in inter-filament bonding in AIBN-

treated samples because the thermal environment of the layer is insufficient to react

AIBN with the butadiene present.

When treated with DADPM solution, samples with pause times of 30 minutes and

1 hour displayed marked improvement in interfacial adhesion over that of neat ABS.

This improvement indicates that DADPM chemically crosslinks the ABS layers, most

likely through reactive functional groups. Pure ABS does not contain monomers with

functional groups capable of reacting with DADPM. When exposed to heat and air,

however, the polybutadiene (PB) segments of the ABS filament will undergo thermo-

oxidative degradation to carboxyl groups. One study by Shimada and Kabuki

demonstrated that the thermal oxidation of PB occurs at temperatures as low as 70-90

oC.21 The process by which this occurs involves the formation of hydroperoxide radicals

which collapse to hydroxyl and carboxyl groups. Since the samples in this experiment

16
were printed at 210 oC, the temperatures were sufficiently high to induce thermo-

oxidative degradation of the PB monomers. If PB degradation occurs, the carboxyl

groups can react with the terminal amine groups of DADPM to form covalent bonds

between the deposited layers, probably via an amidization reaction.

Post-polymerization modification of ABS

The targeted structures for the cysteamine and DODT-modified ABS are shown

in Figure 8.

Figure 8: Presents the targeted structures of cysteamine (L)-and DODT (R)-modified ABS in which the thiols have been added to
the double bond of the butadiene within the polymer chain.

1H-NMR spectra obtained from the cysteamine and DODT-modified ABS are presented

in Figures 8 and 9 and compared to that of neat ABS filament (Appendix). In the

spectrum for the neat filament, the methyl region (0.9-2.0 ppm) contains a collection of

peaks associated with proton resonances of the –CH2 groups on the polymer chains.

The broad peak corresponding to the proton resonances of the butadiene component

occurs at 5.25 ppm. Further downfield between 6.5-7.5 ppm in the aromatic region,

there is a cluster of peaks consistent with the deshielded protons of styrene.

17
 Figure 9: Shows the 1H-NMR spectrum of cysteamine-modified ABS.

Figure 9 presents the spectrum obtained for cysteamine-modified ABS. A

qualitative comparison of this spectrum with that of the non-modified ABS indicates that

the three components are still present in the spectrum. Although the styrene peak

remained unchanged as expected, the acrylonitrile and butadiene peaks, which occur in

the regions of 2.0-2.5 ppm and 5.0-5.5 ppm respectively, show a marked decrease in

size. This indicates that butadiene and acrylonitrile were lost in the reaction with

cysteamine. The decrease in peak size suggests that butadiene underwent thiol

modification. If modification occurred, a peak should also be visible consistent with the

chemical shift of the protons of the cysteamine –NH2 group. This is expected to occur in

the 1.5-2.0 ppm region. From the spectrum, this region also corresponds to the

resonances of the protons from the –CH2 groups of the polymer chains. Therefore, the

18
presence of the thiol is indistinguishable in the cysteamine-ABS spectrum due to

overlap with the –CH2 groups.

The spectrum for the DODT-modified ABS is shown in Figure 10. Both the

styrene and acrylonitrile peaks are still prominent but the butadiene peak is no longer

present in the 5.0-5.5 ppm range. The lack of a butadiene peak suggests that butadiene

reacted with DODT. To further reinforce the evidence for a reaction, there are peaks

present at 2.75 ppm and 3.65 ppm that are consistent with the chemical shifts expected

for the proton resonances of the DODT –CH2SH and –OCH2 groups respectively.

Qualitatively, the data suggest that the ABS was modified with DODT via the thiol-ene

click reaction.

Figure 10: Shows the 1H-NMR spectrum for DODT-modified ABS.

19
 % Acrylonitrile % Butadiene % Styrene % Thiol

ABS Filament 25.1 12.2 62.7 0

Cysteamine-modified indeterminate 1.17 62.7 indeterminate

DODT-modified 24.85 0 62.7 12.45

Table 2: Presents a comparison of the percent composition of the cysteamine and DODT-modified ABS with non-modified ABS

To quantify the amount of butadiene lost from the copolymer as well as the

amount of thiol added, the percent compositions for each of the thiol-modified ABS were

calculated from peak integration values and are presented in Table 2. For the ABS

beads utilized in this experiment, acrylonitrile, styrene and butadiene comprise 25.1 %,

62.7 % and 12.2 % of the polymer chain respectively. If all of the butadiene reacted with

the thiol, the percent butadiene composition would be 0% while the thiol would comprise

12.2 % of the ABS. Although the butadiene composition in the cysteamine-modified

ABS decreased from 12.2 % to 1.17 %, quantitative calculations for the amount of thiol

added were not possible due to the extensive peak overlap in the methyl region. In the

DODT-modified ABS, however, the butadiene peak disappeared and the thiol peaks

emerged at 2.75 ppm and 3.65 ppm, corresponding to a 12.45 % composition of the

copolymer. This value is consistent with the expected thiol composition for the modified

ABS if all of the butadiene was reacted and is a strong indicator that the thiol-ene “click”

reaction allowed for effective post-polymerization modification of ABS.

20
Chapter 4: Conclusion

One of the major obstacles to utilizing FDM as an alternative to traditional

manufacturing methods is the anisotropy affecting 3D printed parts. In this work, the

application of a chemical cross-linker between deposited layers of ABS copolymer has

been shown to reduce anisotropy by increasing inter-filament bonding in the z-direction.

The mechanism for this cross-linking is not yet fully understood, however. Therefore,

future studies should characterize the surface of the 3D printed layers to obtain an

understanding of molecular orientation so that we can discover enhanced methods of

chemical cross-linking that will result in improved mechanical properties.

Additionally, covalent modification of ABS was demonstrated through thiol post-

polymerization methods. The disappearance of the butadiene peak in the 1H-NMR

spectra indicates that covalent bonds formed between the thiol and butadiene

component of ABS through a thiol-ene “click” reaction. To further establish that the

butadiene disappeared as a result of the thiol-ene reaction rather than reaction

conditions, it would be necessary to perform the reaction utilizing ABS beads with no

added thiol and then acquire the 1H-NMR spectrum of the product. Butadiene lost

through reaction conditions could then be accounted for in the thiol composition

percentage. By demonstrating that ABS is capable of undergoing post-polymerization

modification, pathways to utilize covalent bond formation between layers during the 3D

printing process are provided, which could also lay a foundation for surface

functionalization of the 3D printed parts. Building on these findings will allow us to

design research to improve properties of 3D printed parts and transition from

prototyping to mass manufacturing plastics using FDM technology.

21
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Appendix

Shows the 1H-NMR spectrum for non-modified ABS.

25