Revista de Ciencias Tecnológicas (RECIT). Universidad Autónoma de Baja California ISSN 2594-1925

Volumen 4 (4): 388-398. Octubre-Diciembre 2021. https://doi.org/10.37636/recit.v44388398

ISSN 2594-1925

388

Polylactic acid/multi walled carbon nanotubes

(PLA/MWCNT) nanocomposite for 3D printing of medical

devices

Nanocomposito ácido poliláctico-nanotubos de carbono multi pared

(PLA/MWCNT) para la impresión 3D de dispositivos médicos

Manuel Alejandro Cardona Salcedo1, Mercedes Teresita Oropeza Guzmán1, Grecia Isis Moreno Grijalva1,

Arturo Zizumbo López2, Juan Antonio Paz González3, Yadira Gochi Ponce1

1Tecnológico Nacional de México/Instituto Tecnológico de Tijuana, Posgrado en Ciencias de la Ingeniería, Blvd. Industrial s/n col.

Mesa de Otay, 22500, Tijuana, Baja California, México

2Centro de Graduados e Investigación en Química, Instituto Tecnológico de Tijuana, Blvd. Industrial s/n col. Mesa de Otay, 22500,

Tijuana, Baja California, México

3Facultad de Ciencias de la Ingeniería y Tecnología, Universidad Autónoma de Baja California. Unidad Valle de las Palmas,

Tijuana, Baja California, México

Corresponding author: Dra. Yadira Gochi Ponce, Tecnológico Nacional de México/Instituto Tecnológico de Tijuana, Posgrado en

Ciencias de la Ingeniería, Blvd. Industrial s/n col. Mesa de Otay, 22500, Tijuana, Baja California, México. E-mail:

yadira.gochi@tectijuana.edu.mx . ORCID: 0000-0002-1590-2432.

Received: November 22 2021 Accepted: November 25 2021 Published: December 8 2021

Abstract. - In recent years, the composite nanomaterials area has had a great development impact in health sciences. Biomaterials depict

as one of the most promising since they are compatible with additive manufacturing (AM) techniques. It is also possible to use them to mold

specific medical parts. Composite nanomaterials have shown good biocompatibility and low toxicity to have benefits equal to or greater than

metals (i.e., Co-Cr alloy). The purpose of this study is to develop a nanocomposite biomaterial (PLA/MWCNTf) from Polylactic Acid (PLA)

and functionalized Multi Walled Carbon Nanotubes (MWCNTf) to evidence its potential application in 3D printing of orthopedic fixation

devices. PLA/MWCNTf nanocomposite was prepared by solution blending technique, incorporating a proportion of 0.5 wt% of MWCNTf to

the PLA matrix. TGA analysis of the PLA/MWCNTf was used to determine the thermal stability, a slight increase was found compared to the

PLA. FTIR spectroscopy confirmed the presence of carboxylic acid groups in the MWCNTf which improves good incorporation of the

nanotubes in the PLA matrix. Additionally, Raman spectroscopy, SEM, and AFM micrographs were used to verify MWCNTf reached the PLA

surface homogeneously. Additive manufacturing preparation was done by extrusion molding of PLA/MWCNTf as well as its 3D printing.

Keywords: Polylactic acid (PLA); Multi walled carbon nanotubes (MWCNT); 3D printing; Biomaterials; Nanocomposites.

Resumen. - En los últimos años el área de los nanomateriales compuestos ha tenido un gran impacto en el desarrollo de las ciencias de la

salud. Los biomateriales se describen como uno de los más prometedores, ya que son compatibles con las técnicas de manufactura aditiva

(AM). También es posible utilizarlos para moldear piezas médicas específicas. Los nanomateriales compuestos han demostrado una buena

biocompatibilidad y baja toxicidad para tener beneficios iguales o superiores a los de los metales (p. ej. aleación de Co-Cr). El propósito de

este estudio es desarrollar un biomaterial nanocomposito (PLA/MWCNTf) a partir de ácido poliláctico (PLA) y nanotubos de carbono multi

pared funcionalizados (MWCNTf) para evidenciar su potencial aplicación en la impresión 3D de dispositivos de fijación ortopédica. El

nanocomposito de PLA/MWCNTf se preparó mediante la técnica de mezclado en solución, incorporando una proporción de 0,5% en peso

de MWCNTf a la matriz de PLA. Se utilizó el análisis TGA de PLA/MWCNTf para determinar la estabilidad térmica, se encontró un ligero

aumento en comparación con el PLA. La espectroscopía FTIR confirmó la presencia de grupos carboxilos en los MWCNTf lo que mejora

una buena incorporación de los nanotubos en la matriz PLA. Además, se utilizó espectroscopía Raman y SEM para verificar que MWCNTf

alcanzara la superficie de PLA de manera homogénea. La preparación de la manufactura aditiva se realizó mediante moldeo por extrusión

de PLA/MWCNTf así como su impresión 3D.

Palabras clave: Ácido poliláctico (PLA); Nanotubos de carbono multi pared (MWCNT); Impresión 3D; Biomateriales; Nanocompositos.

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1. Introduction

Medical devices can be manufactured from a wide

variety of materials using different techniques.

Additive Manufacturing is a processes that allows

us a personalized development of different

medical devices, satisfying the particular needs of

each patient [1], [2]. According to NOM-240-

SSA1-2012, medical devices are manufactured for

the purpose of diagnosing, monitoring or

preventing disease in humans or auxiliary in the

treatment of them and disability, as well as to be

used in the replacement, correction, restoration or

modification of the anatomy or physiological

processes. Medical devices include products in the

following categories: medical equipment,

prostheses, orthesis, functional aids, dental

supplies, surgical materials, among others [3].

Nanocomposite biomaterials are in constant

research and development as they offer better

properties than the materials commercially used in

this area. Different metal alloys are used for the

production of orthopedic prostheses (total hip

replacement, total knee replacement) and also

orthopedic fixation devices, specifically those

used in osteosynthesis procedures (screws, plates,

nails, rods). One of the most widely used metal

alloy is Cobalt-Chromium, however, various

authors and patients have reported adverse effects

caused by this alloy [4].

According to literature, serum cobalt and

chromium concentrations are increased in patients

with prostheses made with this mentioned

material, this condition is known as metallosis.

Campbell et al. [5] shows that some of the effects

caused by high Co concentrations are

periprosthetic soft tissue reactions,

cardiomyopathies and hypothyroidism. In

addition, Green et al. [6] explains the emergence

of neurological abnormalities caused by this

metallosis, among which are: concentration

problems, short term memory deficit,

disorientation in place, neurocognitive deficits,

even dementia, among others. Similarly, other

registered symptoms are loss of weight and

appetite, depression, low energy and metallic

taste.

According to what has been explained,

neurodegenerative problems, cardiopathies and

polyneuropathies are some of the most

dangerous adverse effects that have been

evidenced due to Cobalt-Chromium prostheses

metallosis [6–12]. Due to all these mentioned

consequences, in 2020 cobalt was listed as a

CMR (carcinogenic, mutagenic and toxic for

reproduction). This event generates the need to

develop new alternative materials to Co-Cr.

Biodegradable polymers have been of great

importance in biomedical applications, mainly

due to their high acceptance by the human body

(biocompatibility) and their low toxicity, being

Polylactic Acid (PLA) one of those with best

properties.

PLA being a biopolymer, it does not come from

oil derivatives, instead at an industrial level it is

produced from corn starch. In addition, PLA is

biodegradable and biocompatible polymer.

PLA is also bioabsorbable, due to this fact, it is

used for the manufacture of bioabsorbable

surgical sutures and orthopedic screws, which

do not need to be removed as they are absorbed

by the human body. Also, PLA is the most

widely used material in various additive

manufacturing (AM) processes such as 3D

printing by FDM (Fused Deposition Modeling)

and SLA (Stereolithography). PLA matrix

nanocomposites biomaterials have had a strong

development in recent years, mainly those

reinforced with nanofillers such as carbon

nanostructures (i.e., multi walled and single

walled carbon nanotubes, graphene, graphene

oxide, reduced graphene oxide, carbon dots,

among others) [13-29].

Nanocomposites are manufactured with the

purpose of obtaining better properties (i.e.,

mechanical, electrical, thermal, biological) than

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those of their components alone. All these

improvements give them a wide spectrum of

applications, mainly in the manufacture of cell

scaffolds, prostheses, biosensors, artificial tissues

and drug delivery [31].

Chen, et al. [14] reported that adding graphene

oxide (GO) to a copolymer of PLA-PU (Polylactic

Acid-Polyurethane) notably improves the

mechanical, thermal and biological properties of

the composite compared to the PLA-PU alone.

Also, they used the composite for 3D printing of a

cell scaffold and evaluated its cell viability.

Additionally, Liu et al. [15] manufactured a

surgical suture from a composite of PLA

reinforced with Multi Walled Carbon Nanotubes

(MWCNT), achieving an increase in mechanical

resistance. The nanocomposite they developed

registered also an increase of up to 50% in the

bioabsorption time as well as a 100% in the

strength valid time.

Azizi et al. [23] developed a nanocomposite from

a copolymer of Polypropylene/Polylactic acid

(PP/PLA) with Multiwalled Carbon Nanotubes,

they improved the mechanical strength of the

copolymer as well as its biodegradation time in

soil. They also suggest that this nanocomposite is

a good candidate for use in food packaging. On the

other hand, Spinelli et al. [24] studied the

electromagnetic properties of a nanocomposite of

Polylactic acid (PLA) with Multi Walled Carbon

Nanotubes (MWCNT) and Graphene

Nanoplatelets (GNP). They found an interest

behavior, the electromagnetic efficiency of the

nanocomposite depended on the aspect ratio of the

nanofillers. As mentioned, adding carbon

nanostructures to polymers such as PLA can

improve various properties that can be used in

different applications. In order to avoid the use of

Co-Cr alloy for the manufacture of prostheses. The

purpose of this study is to developed a PLA

nanocomposite biomaterial reinforced with

MWCNT to be used in 3D FDM printing of

orthopedic fixation devices used in

osteosynthesis procedures.

2. Methodology

2.1 Materials

In this research, transparent PLA filament from

Nature Works model Ingeo Biopolymer 3D850

was used as the polymeric matrix of the

nanocomposite. The Multi Walled Carbon

Nanotubes (MWCNT) were synthesized by

spray pyrolysis technique to be used as

reinforcement of the polymeric matrix [32].

Toluene (𝐶7𝐻8), ferrocene (𝐶10𝐻10𝐹𝑒),

chloroform (𝐶𝐻𝐶𝑙3), sulfuric acid (𝐻2𝑆𝑂4),

nitric acid (𝐻𝑁𝑂3) and hydrochloric acid (𝐻𝐶𝑙)

used were from Sigma Aldrich.

2.2 MWCNT synthesis

A Toluene/Ferrocene solution was prepared at

0.1 M, subsequently the solution was

introduced under an inert atmosphere (Ar) to

the synthesis system by a peristaltic pump

SPETEC model PERIMAX with a flow of 10

ml/hr. The synthesis system consists of a

Thermo Scientific Lindberg Blue M oven with

a quartz concentric tube which must be at 850

°C. In addition, an Agilent nebulizer was used

to introduce the Toluene/Ferrocene solution

and a source of Argon (Ar) gas to maintain an

inert atmosphere within the system. Once the

precursor solution entered the oven together

with Ar for 30 minutes, the synthesis was

concluded. Finally, the MWCNT were

extracted manually from the quartz tube with a

metallic rod. Figure 1 shows the carbon

nanotubes synthesis system used.

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Figure 1. MWCNT synthesis system.

2.3 MWCNT modification

In order to obtain a good interaction between the

PLA polymer matrix and the MWCNT, the

nanotubes were functionalized by incorporating

COOH functional groups through an acid

treatment [33]. 100 mg of MWCNT were placed

in a solution of 𝐻2𝑆𝑂4: 𝐻𝑁𝑂3 in a ratio of 3:1 vol.

for 5 hours in an ultrasonic bath, then 10 ml of HCl

1M was added and they were left to sonicate for 30

minutes. Subsequently they were diluted in

deionized water and dried with a vacuum pump.

The MWCNT functionalized with carboxylic

acids (COOH) were called MWCNTf.

2.4 PLA/MWCNTf nanocomposite development

The nanocomposite biomaterial developed was

called PLA/MWCNTf, was synthesized using

solution blending method [34]. The PLA was

dispersed in chloroform under magnetic stirring.

Similarly, the MWCNTf were dispersed in

chloroform in an ultrasonic bath for 1 hour.

Subsequently, both dispersions were mixed. The

dispersions of PLA and MWCNTf before and after

mixing are shown in Figure 2. Once the dispersion

of PLA and MWCNTf was homogenized, it was

dried at 50 °C for 24 hrs.

Figure 2. a) PLA dispersed in chloroform, b) MWCNTf

dispersion c) PLA/MWCNTf dispersion.

Different characterizations were carried out to

the elaborated materials. Fourier Transform

Infrared Spectroscopy (FTIR) and Raman

Spectroscopy were obtained with a Shimadzu

IRSpirit and Thermo Scientific DXR Smart

Raman 780 nm, respectively. For

Thermogravimetric Analysis (TGA) a TA

Instruments model SDT 2960 Simultaneous

DSC-TGA was used. Scanning Electron

Microscopy (SEM) micrographs were obtained

with a TESCAN model VEGA3 microscope

and FESEM JEOL. Atomic Force Microscopy

(AFM) analysis was performed on a Nanosurf

Easy Scan equipment.

2.4 PLA/MWCNTf nanocomposite molding

To prepare the nanocomposite material for 3D

Printing, the synthesized nanocomposite film

(PLA/MWCNTf) was subjected to a molding

process which consisted of several steps. The

film was crushed using a blender, subsequently

the crushed nanocomposite was entered into a

Filabot EX2 extrusion equipment. The

extrusion machine was set at 170 °C to produce

the 1.75 mm diameter nanocomposite filament,

which is the most standard dimension used in

3D printers. Figure 3 shows the extrusion

molding process of the PLA/MWCNTf.

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Figure 3. PLA/MWCNTf nanocomposite extrusion molding

process.

3. Results

3.1 FTIR spectroscopy

Figure 4 shows the spectra of the PLA polymer

matrix and the PLA/MWCNTf nanocomposite.

The stretching band of 1747 cm-1 and a broad band

between 3050-3142 cm-1 correspond to the

carboxyl groups (COOH) proper to the structure of

PLA, while at 1181 cm-1 corresponds to CO bonds

of the steric chain matrix. Furthermore, in the same

figure the FTIR spectra of the MWCNT and

MWCNTf are presented, the wave number value

of 1531 cm-1 corresponds to the C=C bonds of the

structure of carbon nanotubes while the value of

1731 cm-1 correspond to the carbonyl CO groups

from COOH added to the MWCNTf.

Figure 4. FTIR spectrums of: a) PLA, b) PLA/MWCNTf, c)

MWCNT and d) MWCNTf.

3.2 Raman spectroscopy

Raman spectroscopy is a very useful

characterization technique since it is non-

destructive with the sample and valuable

information can be extracted from this

spectroscopic technique. Multi Walled Carbon

Nanotubes have a characteristic spectrum made

up of two bands, D and G. The relationship

between the intensity of both bands (D/G) give

information about the number of defects that

the MWCNT have, the higher this ratio, the

greater the number of defects the nanotubes will

have [35]. The D band is located at an

approximate wave number value of 1300 cm-1,

while the G band is at an approximate value of

1600 cm-1.

In Figure 5, D band presents greater intensity

than the G, this is due to the defects that were

generated in the nanotubes by the oxidative

functionalization. Similarly, the spectrum of

Polylactic Acid has several characteristic peaks,

some of them are at 850 cm-1, 1400 cm-1, 1750

cm-1, 2900 cm-1. The Raman spectrum of a

composite material clearly results in the sum of

the spectra of the raw materials, showing a good

incorporation of nanometric reinforcement into

the polymeric matrix.

Most of all the characteristic peaks of each

material is shown in the nanocomposite

spectrum, including a new peak approximately

at 2650 cm-1suggesting binding forces between

PLA and MWCNTf (see Figure 5).

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Figure 5. Raman spectra of: a) PLA, b) MWCNTf, c)

PLA/MWCNTf.

3.4 Scanning Electron Microscopy (SEM)

Figure 6 shows MWCNT, MWCNTf and

PLA/MWCNTf. Functionalized Multi Walled

Carbon Nanotubes (b) show less agglomeration

than the pristine Nanotubes (a), this behavior is

consequence of the acid modification

(functionalization). Using ImageJ, an open-source

software, the calculated diameter of the MWCNTf

was 28-60 nm, with an average diameter of 48 nm.

The way in which MWCNTf physically interact

with the polymeric matrix of Polylactic Acid

(PLA) is shown in Figure 6 (c), it can be seen how

the nanotubes are embedded within the polymer.

Figure 6. SEM micrograph of a) MWCNT, b) MWCNTf,

c) PLA/MWCNTf.

3.3 Thermogravimetric Analysis (TGA)

Functionalized Multi Walled Carbon

Nanotubes (MWCNTf) were analyzed in an

inert atmosphere (Nitrogen) with a temperature

of 0-800 °C and a heating ramp of 10 °C/min,

while Polylactic Acid and PLA/MWCNTf

nanocomposite were analyzed in air

atmosphere at 0-600 °C and a heating ramp of

10 °C/min. Figure 7 shows MWCNTf

thermogram, which has a decrease in their

thermal stability due to the oxidative treatment

and carboxyl functionalization.

Simultaneously, Figure 7 also shows the

thermogram of PLA and PLA/MWCNTf. The

nanocomposite registered an increase in the

thermal stability at different temperature

intervals compared to the polymer (PLA), this

enhancement is due to the incorporation of the

MWCNTf to the polymeric matrix which allow

a delay in the weight loss of the material.

Additionally, Table 1 shows the temperature

value at which the materials lose a specific

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weight loss percentage. This thermal stability

improvement extends the application area of the

nanocomposite, however in this study the material

is proposed to be used at physiological

temperatures (37 °C).

Figure 7. TGA thermograms: a) PLA, b) MWCNTf, c)

PLA/MWCNTf.

Table 1. TGA weight loss values.

Sample

T10%

weight

loss

(°C)

T25%

weight

loss

(°C)

T50%

weight

loss

(°C)

T75%

weight

loss

(°C)

PLA

302

329.7

344.3

355.4

PLA/MWCN

315.

336.0

349.3

358.8

3.5 Atomic Force Microscopy (AFM)

Figure 8 presents the recorded AFM micrograph of

the PLA/MWCNTf nanocomposite surface, it

shows the surface generated by the incorporation

between the polymeric matrix (PLA) and the nano

reinforcement (MWCNTf). Using ImageJ, the

calculated average diameter of the circular bumps

present on the surface was 57.16 nm, which

coincide within the range of the diameter of the

carbon nanotubes. It is proposed that these bumps

are produced by the incorporation of the nano-

reinforcement within the polymeric matrix.

Figure 8. AFM micrograph of PLA/MWCNTf.

3.6 3D Printing Extrusion

The dimensions of the extruded PLA/MWCNTf

nanocomposite filament were measured with a

vernier caliper, obtaining a result of 1.75 mm in

diameter. Subsequently, the filament was

introduced into an Anet ET4 3D printer with a

0.4 mm extruder nozzle at a temperature of 220

° C, thin filaments whose dimension was 0.48

mm were obtained. Figure 9 shows the extruded

filament (a) with its diameter measure(b),

additionally the 3D printed filament (c) and its

diameter measure (d).

Figure 9. PLA/MWCNTf nanocomposite extruded

filament (a-b) and 3D printed filament (c-d).

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4. Conclusions

Solution blending technique was successful to

developed a PLA/MWCNTf 0.5 wt%

nanocomposite for additive manufacturing (3D

printing). In addition, through different

characterizations some properties of the

synthesized biomaterial were studied and

determined complementing what has already been

reported in the literature. The nanocomposite was

successfully extruded and 3D printed, additionally

it presented an increase in its thermal stability

compared with the polymeric matrix (PLA). An

interaction between the nanofillers (Multi Walled

Carbon Nanotubes) and the polymer (PLA) was

determined by the Raman spectroscopy SEM and

AFM micrographs. Some of the techniques and

procedures that will soon be used for

PLA/MWCNTf are 3D printing of the orthopedic

device and biocompatibility tests (hemolytic and

cell viability).

5. Acknowledgements

To TecNM Project Number: 10716.21-P,

Tecnológico Nacional de México/IT de Tijuana

and CONACYT.

6. Authorship and contribution

Manuel Alejandro Cardona Salcedo: Project

conceptualization, manuscript redaction-edition,

methodology, research, analysis and validation.

Mercedes Teresita Oropeza Guzmán: Revision,

redaction, project supervision-administration,

methodology and analysis. Grecia Isis Moreno

Grijalva: Methodology and analysis. Zizumbo

López Arturo: Data analysis, validation. Juan

Antonio Paz González: Methodology and analysis.

Gochi Ponce Yadira: Redaction, project

supervision, analysis.

References

[1] L. M. Ricles, J. C. Coburn, M. Di Prima, and

S. S. Oh, "Regulating 3D-printed medical

products," Sci. Transl. Med., vol. 10, no.

461, pp. 1-7, 2018.

https://doi.org/10.1126/scitranslmed.aan6

521.

[2] M. Di Prima, J. Coburn, D. Hwang, J. Kelly,

A. Khairuzzaman, and L. Ricles,

"Additively manufactured medical

products - the FDA perspective," 3D Print.

Med., vol. 2, no. 1, pp. 4-9, 2016.

https://doi.org/10.1186/s41205-016-0005-

[3] Norma Oficial Mexicana, NOM-240-SSA1-

2011, Instalación y operación de la

tecnovigilancia. 2012, p. 13.

http://www.dof.gob.mx/normasOficiales/4

600/salud/salud.htm

[4] J. J. Devlin, A. C. Pomerleau, J. Brent, B.

W. Morgan, S. Deitchman, and M.

Schwartz, "Clinical Features, Testing, and

Management of Patients with Suspected

Prosthetic Hip-Associated Cobalt Toxicity:

A Systematic Review of Cases," J. Med.

Toxicol., vol. 9, no. 4, pp. 405-415, 2013.

https://doi.org/10.1007/s13181-013-0320-

[5] J. R. Campbell and M. P. Estey, "Metal

release from hip prostheses: Cobalt and

chromium toxicity and the role of the

clinical laboratory," Clin. Chem. Lab.

Med., vol. 51, no. 1, pp. 213-220, 2013.

https://doi.org/10.1515/cclm-2012-0492.

[6] B. Green, E. Griffiths, and S. Almond,

"Neuropsychiatric symptoms following

metal-on-metal implant failure with cobalt

and chromium toxicity," BMC Psychiatry,

vol. 17, no. 1, pp. 1-5, 2017.

396 ISSN 2594-1925

Revista de Ciencias Tecnológicas (RECIT). Volumen 4 (4): 388-398

https://doi.org/10.1186/s12888-016-1174-1.

[7] L. Leyssens, B. Vinck, C. Van Der Straeten, F.

Wuyts, and L. Maes, "Cobalt toxicity in

humans-A review of the potential sources and

systemic health effects," Toxicology, vol.

387, pp. 43-56, 2017.

https://doi.org/10.1016/j.tox.2017.05.015.

[8] A. C. Cheung et al., "Systemic cobalt toxicity

from total hip arthroplasties," Bone Jt. J., vol.

98B, no. 1, pp. 6-13, 2016.

https://doi.org/10.1302/0301-

620X.98B1.36374

[9] A. Vaicelyte, C. Janssen, M. Le Borgne, and B.

Grosgogeat, "Cobalt-Chromium Dental

Alloys: Metal Exposures, Toxicological

Risks, CMR Classification, and EU

Regulatory Framework," Crystals, vol. 10, no.

12, p. 1151, 2020.

https://doi.org/10.3390/cryst10121151.

[10] T. Ikeda, K. Takahashi, T. Kabata, D.

Sakagoshi, K. Tomita, and M. Yamada,

"Polyneuropathy caused by cobalt-chromium

metallosis after total hip replacement,"

Muscle and Nerve, vol. 42, no. 1, pp. 140-143,

2010. https://doi.org/10.1002/mus.21638.

[11] A. W. Schaffer, A. Pilger, C. Engelhardt, K.

Zweymueller, and H. W. Ruediger, "Increased

blood cobalt and chromium after total hip

replacement," J. Toxicol. - Clin. Toxicol., vol.

37, no. 7, pp. 839-844, 1999.

https://doi.org/10.1081/CLT-100102463.

[12] W. Apel, D. Stark, A. Stark, S. O'Hagan, and

J. Ling, "Cobalt-chromium toxic retinopathy

case study," Doc. Ophthalmol., vol. 126, no.

1, pp. 69-78, 2013.

https://doi.org/10.1007/s10633-012-9356-8.

[13] B. Scharf et al., "Molecular analysis of

chromium and cobalt-related toxicity," Sci.

Rep., vol. 4, no. 1, p. 5729, 2014.

https://doi.org/10.1038/srep05729.

[14] Q. Chen, J. D. Mangadlao, J. Wallat, A. De

Leon, J. K. Pokorski, and R. C. Advincula,

"3D printing biocompatible

polyurethane/poly(lactic acid)/graphene

oxide nanocomposites: Anisotropic

properties," ACS Appl. Mater. Interfaces,

vol. 9, no. 4, pp. 4015-4023, 2017.

https://doi.org/10.1021/acsami.6b11793.

[15] S. Liu et al., "Degradation behavior in vitro

of carbon nanotubes (CNTs)/poly (lactic

acid) (PLA) composite suture," Polymers

(Basel)., vol. 11, no. 6, 2019.

https://doi.org/10.3390/polym11061015.

[16] M. Gong, Q. Zhao, L. Dai, Y. Li, and T.

Jiang, "Fabrication of polylactic

acid/hydroxyapatite/graphene oxide

composite and their thermal stability,

hydrophobic and mechanical properties," J.

Asian Ceram. Soc., vol. 5, no. 2, pp. 160-

168, 2017.

https://doi.org/10.1016/j.jascer.2017.04.00

[17] P. O. Andrade, M. A. V. M. Grinet, M. M.

Costa, A. M. E. Santo, F. R. Marciano, and

A. O. Lobo, "Poly (Lactic Acid) Fine

Fibers Containing a Low Content of

Superhydrophilic Multi-Walled Carbon

Nanotube Graphene Oxide Hybrid as

Scaffolds for Biological Applications,"

Macromol. Mater. Eng., vol. 303, no. 11,

pp. 1-11, 2018.

https://doi.org/10.1002/mame.201800317.

[18] F. Alam, V. R. Shukla, K. M. Varadarajan,

and S. Kumar, "Microarchitected 3D

printed polylactic acid (PLA)

nanocomposite scaffolds for biomedical

applications," J. Mech. Behav. Biomed.

Mater., vol. 103, p. 103576, 2020.

397 ISSN 2594-1925

Revista de Ciencias Tecnológicas (RECIT). Volumen 4 (4): 388-398

https://doi.org/10.1016/j.jmbbm.2019.103576

[19] C. H. Tsou et al., "Antibacterial property and

cytotoxicity of a poly (lactic acid)/nanosilver-

doped multiwall carbon nanotube

nanocomposite," Polymers (Basel)., vol. 9,

no. 3, 2017.

https://doi.org/10.3390/polym9030100.

[20] A. F. Ahmad et al., "Biodegradable poly

(lactic acid)/poly (ethylene glycol) reinforced

multi-walled carbon nanotube nanocomposite

fabrication, characterization, properties, and

applications," Polymers (Basel)., vol. 12, no.

2, pp. 1-22, 2020.

https://doi.org/10.3390/polym12020427.

[21] G. Spinelli et al., "Effects of filament

extrusion, 3D printing and hot-pressing on

electrical and tensile properties of poly

(Lactic) acid composites filled with carbon

nanotubes and graphene," Nanomaterials, vol.

10, no. 1, 2020.

https://doi.org/10.3390/nano10010035.

[22] L. Yang et al., "Effects of carbon nanotube on

the thermal, mechanical, and electrical

properties of PLA/CNT printed parts in the

FDM process," Synth. Met., vol. 253, no.

December 2018, pp. 122-130, 2019.

https://doi.org/10.1016/j.synthmet.2019.05.0

08.

[23] S. Azizi, M. Azizi, and M. Sabetzadeh, "The

role of multiwalled carbon nanotubes in the

mechanical, thermal, rheological, and

electrical properties of pp/pla/mwcnts

nanocomposites," J. Compos. Sci., vol. 3, no.

3, pp. 1-15, 2019.

https://doi.org/10.3390/jcs3030064.

[24] G. Spinelli et al., "Morphological, rheological

and electromagnetic properties of

nanocarbon/poly(lactic) acid for 3D printing:

Solution blending vs. melt mixing," Materials

(Basel)., vol. 11, no. 11, 2018.

https://doi.org/10.3390/ma11112256.

[25] M. Kaseem, K. Hamad, F. Deri, and Y. G.

Ko, "A review on recent researches on

polylactic acid/carbon nanotube

composites," Polym. Bull., vol. 74, no. 7,

pp. 2921-2937, 2017.

https://doi.org/10.1007/s00289-016-1861-

[26] Y. Shen et al., "Chemical and thermal

reduction of graphene oxide and its

electrically conductive polylactic acid

nanocomposites," Compos. Sci. Technol.,

vol. 72, no. 12, pp. 1430-1435, 2012.

https://doi.org/10.1016/j.compscitech.201

2.05.018.

[27] C. Hu et al., "Comparative assessment of

the strain-sensing behaviors of polylactic

acid nanocomposites: reduced graphene

oxide or carbon nanotubes," J. Mater.

Chem. C, vol. 5, no. 9, pp. 2318-2328,

2017.

https://doi.org/10.1039/C6TC05261D.

[28] C. Liu, J. Shen, K. W. K. Yeung, and S. C.

Tjong, "Development and Antibacterial

Performance of Novel Polylactic Acid-

Graphene Oxide-Silver Nanoparticle

Hybrid Nanocomposite Mats Prepared by

Electrospinning," ACS Biomater. Sci.

Eng., vol. 3, no. 3, pp. 471-486, 2017.

https://doi.org/10.1021/acsbiomaterials.6b

00766.

[29] A. M. Pinto, J. Cabral, D. A. P. Tanaka, A.

M. Mendes, and F. D. Magalhães, "Effect

of incorporation of graphene oxide and

graphene nanoplatelets on mechanical and

gas permeability properties of poly (lactic

acid) films," Polym. Int., vol. 62, no. 1, pp.

33-40, 2013.

https://doi.org/10.1002/pi.4290.

398 ISSN 2594-1925

Revista de Ciencias Tecnológicas (RECIT). Volumen 4 (4): 388-398

[30] B. W. Chieng, N. A. Ibrahim, W. M. Z. W.

Yunus, M. Z. Hussein, Y. Y. Then, and Y. Y.

Loo, "Effects of graphene nanoplatelets and

reduced graphene oxide on poly (lactic acid)

and plasticized poly (lactic acid): A

comparative study," Polymers (Basel)., vol. 6,

no. 8, pp. 2232-2246, 2014.

https://doi.org/10.3390/polym6082232.

[31] K. Tappa et al., "3D printing custom bioactive

and absorbable surgical screws, pins, and

bone plates for localized drug delivery," J.

Funct. Biomater., vol. 10, no. 2, 2019.

https://doi.org/10.3390/jfb10020017.

[32] A. Aguilar-Elguézabal, W. Antúnez, G.

Alonso, F. P. Delgado, F. Espinosa, and M.

Miki-Yoshida, "Study of carbon nanotubes

synthesis by spray pyrolysis and model of

growth," Diam. Relat. Mater., vol. 15, no. 9,

pp. 1329-1335, 2006.

https://doi.org/10.1016/j.diamond.2005.10.01

[33] L. S. Tejeda Aguayo, "Síntesis de

nanotubos de carbono de pared múltiple

(MWCNT) funcionalizados con el ácido

2,3-dihidroxibenzoico selectivo al Fe3+

como tratamiento potencial de talasemia",

tesis de maestría, CGIQ., Instituto

Tecnológico de Tijuana, Tijuana, México,

2018.

[34] A. V. Rane, K. Kanny, V. K. Abitha, and

S. Thomas, "Methods for Synthesis of

Nanoparticles and Fabrication of

Nanocomposites," in Synthesis of

Inorganic Nanomaterials, Elsevier Ltd.,

2018, pp. 121-139.

https://doi.org/10.1016/B978-0-08-

101975-7.00005-1.

[35] J. H. Lehman, M. Terrones, E. Mansfield,

K. E. Hurst, and V. Meunier, "Evaluating

the characteristics of multiwall carbon

nanotubes," Carbon N. Y., vol. 49, no. 8,

pp. 2581-2602, 2011.

https://doi.org/10.1016/j.carbon.2011.03.0

28.

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