Development of A Novel Polycrystalline Diamond Master Thesis Uenf

FEDERAL UNIVERSITY OF RIO GRANDE DO NORTE
TECHNOLOGY CENTER (CT)

CENTER OF EXACT AND EARTH SCIENCES (CCET)
MATERIALS SCIENCE AND ENGINEERING

POSTGRADUATE PROGRAM
MASTER’S THESIS
Development of a novel polycrystalline diamond

composite using tantalum as a binder
Regina Bertília Dantas de Medeiros
Advisor: Prof. Dr. Uílame Umbelino Gomes

Co-Advisor: Prof. Dr. Meysam Mashhadikarimi
Natal – RN, Brazil

2021
2
REGINA BERTÍLIA DANTAS DE MEDEIROS
Development of a novel polycrystalline diamond

composite using tantalum as a binder
Master's thesis presented to the Materials Science

and Engineering Postgraduate Program at the
Federal University of Rio Grande do Norte, as part
of the requirements for obtaining a Master’s
degree in Materials Science and Engineering.
Advisor: Prof. Dr. Uílame Umbelino Gomes

Co-Advisor: Prof. Dr. Meysam Mashhadikarimi
Natal– RN, Brazil

2021
Regina Medeiros, 2021 PPgCEM/UFRN

Universidade Federal do Rio Grande do Norte - UFRN
Sistema de Bibliotecas - SISBI
Catalogação de Publicação na Fonte. UFRN - Biblioteca Central Zila Mamede
Medeiros, Regina Bertília Dantas de.

Development of a novel polycrystalline diamond composite
using tantalum as a binder / Regina Bertília Dantas de Medeiros.
- 2021.
100f.: il.
Dissertação (Mestrado) - Universidade Federal do Rio Grande

do Norte, Centro de Ciências Exatas e da Terra, Programa de Pós-
Graduação em Ciência e Engenharia de Materiais, Natal, 2021.
Orientador: Dr. Uílame Umbelino Gomes.
Coorientador: Dr. Meysam Mashhadikarimi.
1. PCD - Dissertação. 2. Tribology - Dissertação. 3. High

Pressure-High Temperature sintering - Dissertação. 4. Powder
Technology - Dissertação. 5. Cutting tools - Dissertação. I.
Gomes, Uílame Umbelino. II. Mashhadikarimi, Meysam. III. Título.
RN/UF/BCZM CDU 620.1
Elaborado por RAIMUNDO MUNIZ DE OLIVEIRA - CRB-15/429

5
Dedicated to all scientists, researchers and

students looking for knowledge. May you
find some of what you're searching for in
this work.

6
ACKNOWLEDGMENT
To begin with, I would like to express my huge and equal thanks to my advisor Prof.
Uílame Umbelino Gomes, and my co-advisor Prof. Meysam Mashhadikarimi, for guiding
and supporting me over this challenging journey. I acknowledge your leadership, trust,
and motivations, which significantly contributed to discovering my true passion for
research and science.
I am deeply grateful to Prof. Marcello Filgueira, for giving me the amazing opportunity
to work at the State University of North Fluminense (UENF), and for all constant support
either personally or even at a distance. Your suggestions and tutoring were extremely
valuable to the development of this project.
I would like to thank the Coordination for the Improvement of Higher Education
Personnel (CAPES) foundation and the Federal University of Rio Grande do Norte
(UFRN) for supporting this project, and for providing all the essential tools to undertake
this degree. The Brazilian public and high-quality education resist, even in such harsh
times.
I am grateful to Prof. Rubens Maribondo do Nascimento and Prof.ª Alessandra Agna

Araújo dos Santos for your guidance, time and expert opinion in evaluating and
improving this research.
I would especially like to express my eternal and unconditional gratitude to my family.

To my parents and siblings, thank you for all the encouragement, support and love, and
for understanding that the physical distance was too necessary. To my love, Ramon, thank
you for always be there, for teaching me to never give up, and to constantly remind me
that I would never ever be alone.
All my gratitude to my wonderful Diamond Group, especially to my dear friends Diego

Gurgel and Lucas Barreto. Thank you for all the good moments, laughter, advice,
encouragement, and incredible inspirations. With you two, I learned that everything is
worthwhile if the soul is not small.
I acknowledge all the team of Advanced Materials Laboratory (LAMAV/UENF),

especially to Renan Guimarães, for all their support and technical assistance during my
stay in Campos dos Goytacazes.

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I would like to offer my special thanks to all the team of Ceramic Materials and Special
Metals Laboratory (LMCME/UFRN). Thank you to all colleagues with who I could share
great coffee break moments, and who helped me directly or indirectly throughout my
master's period.
I extend my sincere thanks to the technicians of Structural Characterization of Materials

Laboratory (LCEM/UFRN), Igor Zumba and Carla Laize, and to the Study Group of
Tribology and Structural Integrity (GET/UFRN), especially to Gustavo Henriques, for
their help and assistance to execute the microstructural and tribological characterization
of this work, even during a pandemic scenario.
Finally, I would like to thank you, dear reader, for the prestige of your attention. Hope
this study may help with your queries.

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“A diamond is a chunk of coal that did well under pressure”

(Henry Kissinger)

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ABSTRACT
Polycrystalline diamond (PCD) is widely applied in the cutting and drilling industries due
to its excellent mechanical properties. Currently, several researchers have been studying
the use of different binders in its manufacturing, seeking to improve their properties and
reduce the use of traditional metals that are harmful to human health and the environment.
This work aimed to study the applicability of tantalum as a novel binding agent of PCD.
The products developed here were processed using powder metallurgy and High
Pressure-High Temperature (HPHT) sintering. The effect of different tantalum
concentrations (2.5, 5.0, 7.5, and 10.0 wt. %) was investigated using X-ray diffraction
(XRD), Confocal Microscopy, Density measurement, Particle Size Analysis, and
Scanning Electron Microscopy (SEM). Mechanical properties and failure behavior were
employed to evaluate the products. The PCD-Ta system was also tribologically tested
against ferrous and ceramic materials, in order to simulate their applicability in industrial
machining conditions. The results suggest that increasing Ta quantity on PCD mixtures
promoted reduction of milling contaminations and enhanced the mechanical properties of
the as-sintered bodies by modifying the fracture mechanism predominance. No
occurrence of chemical reactions between the two compounds was observed on the
milling, but the formation of TaC resulting from a reaction between the free carbon and
the metallic Ta was identified on all as-sintered compositions. The PCD-Ta ratio directly
influences the tribological behavior of the present system with ceramic and ferrous
materials, and severest wear was provoked by samples with the lowest binder content.
Furthermore, abrasive and adhesive were the predominant wear mechanisms detected in
all studied compositions. Finally, the overall microstructural, mechanical, and
tribological outcomes demonstrated that the developed composites presented satisfactory
performance, which indicates that tantalum can be a viable alternative to act as a PCD
binder.
Keywords: PCD, Tantalum, Tribology, High Pressure-High Temperature sintering,

Powder Technology, Cutting tools

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RESUMO
O diamante policristalino (PCD) é um material amplamente aplicado nas indústrias de

corte e perfuração devido às suas excelentes propriedades mecânicas. Atualmente,
diversos pesquisadores tem estudado a utilização de diferentes ligantes em sua fabricação,
buscando melhorar suas propriedades e reduzir o uso de metais tradicionais que são
prejudiciais à saúde humana e ao meio ambiente. Este trabalho teve como objetivo estudar
a aplicabilidade do tântalo como novo agente ligante do PCD. Os produtos aqui
desenvolvidos foram processados por metalurgia do pó e sinterização via Altas Pressões-
Altas Temperaturas (HPHT). O efeito de diferentes concentrações de tântalo (2.5, 5.0,
7.5, e 10.0% em peso) foi investigado usando Difração de Raios-X (DRX), Microscopia
Confocal, Densimetria, Análise de Tamanho de Partícula e Microscopia Eletrônica de
Varredura (MEV). Propriedades mecânicas e análise de falha foram empregadas para
avaliar os produtos. O sistema PCD-Ta também foi testado tribologicamente contra
materiais ferrosos e cerâmicos, a fim de simular condições de aplicabilidade na usinagem
industrial. Os resultados sugerem que o aumento da quantidade de Ta nas misturas com
PCD promoveu redução de contaminações de moagem, e melhorou as propriedades
mecânicas dos corpos sinterizados, modificando a predominância dos mecanismos de
fratura. Não houve ocorrência de reações químicas entre os dois compostos na moagem,
mas a formação de TaC, resultante da reação entre o carbono livre e o Ta metálico, foi
identificada em todas as composições sinterizadas. A razão PCD/Ta influenciou
diretamente o comportamento tribológico do presente sistema contra materiais cerâmicos
e ferrosos, e desgastes mais severos foram provocados por amostras com menor teor de
ligante. Por fim, os resultados microestruturais, mecânicos e tribológicos demonstraram
que os compósitos desenvolvidos apresentaram uma performance satisfatória, indicando
que o tântalo pode ser uma alternativa viável para atuar como ligante do PCD.
Palavras-chave: PCD, Tântalo, Tribologia, Sinterização via Altas Pressões-Altas

Temperaturas, Tecnologia dos pós, Ferramentas de corte.

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LIST OF PUBLICATIONS
Medeiros, R. B. D.; Barreto, L.P.P.; Gurgel, D. P.; Mashhadikarimi, M.; Guimarães

R.D.S.; Filgueira, M.; Gomes, U.U. Study of tantalum as an alternative binder of
polycrystalline diamond. International Journal of Refractory Metals and Hard Materials,
2021, 99: 105587. https://doi.org/10.1016/j.ijrmhm.2021.105587.
Medeiros, R. B. D.; Barreto, L.P.P.; Gurgel, D. P.; Mashhadikarimi, M.; Filgueira, M.;
Gomes, U.U. Tribological behavior of Polycrystalline Diamond-Tantalum composites.
2021. (under review)
Medeiros, R. B. D.; Gurgel, D. P.; Barreto, L.P.P.; Mashhadikarimi, M.; Filgueira, M.;
Gomes, U.U. Wear performance of polycrystalline diamond – tantalum composites tested
against granite. 2021. (under review)
Medeiros, R. B. D.; Figueiredo Filho, J. M.; Mashhadikarimi, M.; Gomes, U.U. Diamond
integrated coating by electroplating process - An overview. Ampliação e aprofundamento
de conhecimentos nas áreas das engenharias 3 Atena, 2020, p. 59-69. doi
10.22533/at.ed.8972017095
PATENTS
Medeiros, R.B.D.; Barreto, L.P.P.; Mashhadikarimi, M.; Filgueira, M.; Gomes, U.U.;
Gurgel, D.P.; Rodrigues, M.A.L.O. Patent BR 10,2020,008103: "Polycrystalline
diamond with addition of pure tantalum as a binder " (In Portuguese), April 23, 2020.
CO-AUTHORED PUBLICATIONS
Gurgel, D. P.; Medeiros, R. B. D.; Barreto, L.P.P.; Mashhadikarimi, M.; Guimarães

R.D.S.; Filgueira, M.; Bichler L.; Gomes, U.U. Pin-on-disc dry sliding study of PCD-Nb
composites against ferrous and non-ferrous materials. 2021. (under preparation)
Gurgel, D. P.; Medeiros, R. B. D.; Barreto, L.P.P.; Mashhadikarimi, M.; Filgueira, M.;
Bichler L.; Gomes, U.U. Study on the densification of different PCD particle shapes using
different concentrations of micro and nanosized Nb as a binder. 2021. (under preparation)
Mashhadikarimi, M., Medeiros, R.B.D., Barreto, L.P., Gurgel, D.P., Gomes, U.U.,
Filgueira, M. Development of a novel triple-layer polycrystalline diamond compact.
Diamond and Related Materials. 2020, Nov 19: 108182.
https://doi.org/10.1016/j.diamond.2020.108182
Barreto, L.P.P.; Mashhadikarimi, M.; Rodrigues, M.A.L.O.; Gurgel, D.P.; Gomes, U.U.;
Filgueira, M.; Medeiros, R.B.D. Preparation and characterization of sintered
polycrystalline diamond (PCD) with 15-wt% Nb binder. Diamond and Related Materials,
v. 106, p. 107867, 2020. https://doi.org/10.1016/j.diamond.2020.107867

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LIST OF ABREVIATIONS AND NOMENCLATURE
A12O3 – Alumina
ASTM – American Society for Testing and Materials
cBN – Cubic Boron Nitride
Co – Cobalt
CO – Carbon Monoxide
CO2 – Carbon Dioxide
CoF – Coefficient of Friction
Cu – Cooper
CVD – Chemical Vapor Deposition
Di – Diamond
EDS – Energy Dispersive Spectroscopy
Fe – Iron
g/cm3 – grams per cubic centimeter
GPa – Giga Pascal
HCl – Hydrochloric acid
HFCVD – Hot Filament Chemical Vapor Deposition
HNO3 – Nitric acid
HPHT – High Pressure High Temperature Process
HV - Hardness Vickers
K – Degree Kelvin
min – Minute
MPa – Mega Pascal
Nb – Niobium
Ni – Nickel
PCD – Polycrystalline diamond
PDC – Polycrystalline diamond compact
TSP – Thermally Stable Polycrystalline Diamond Composite
SEM – Scanning Electron Microscopy

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SiC – Silicon carbide

Si3N4 – Silicon nitride
Ta – Tantalum
Ta2O5 – Tantalum pentoxide
TaC – Tantalum carbide
TiC – Titanium carbide
u. a. – Dimensionless units
WC – Tungsten carbide
WC/Co – Hardmetal
XRD – X-Ray diffraction
μm – micrometer
°C – Degree Celsius

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LIST OF FIGURES
Figure 1: Some carbon allotropes: (a) Diamond, (b) graphite, (c) lonsdaleite, Fullerenes:
(d) C60 (buckyball), (e) C540, (f) C70, (g) amorphous carbon, (h) single-walled carbon
nanotube. ........................................................................................................................ 26
Figure 2: The atomic structure of graphite. The dashed lines indicate secondary forces
between the graphite planes. ........................................................................................... 27
Figure 3: The atomic structure of the diamond. ............................................................ 28
Figure 4: Diamond crystal for optical applications. ...................................................... 30
Figure 5: PCD for detector device, manufactured by CVD .......................................... 30
Figure 6: Representation of a Polycrystalline Diamond Compact tool. ........................ 31
Figure 7: Lapidary Diamond Core Drill Bits. ............................................................... 31
Figure 8: Inserts of polycrystalline diamond. ................................................................ 31
Figure 9: PDC Drill Bits. ............................................................................................... 32
Figure 10: Hardness versus toughness for some conventional cutting tool materials. .. 33
Figure 11: Carbon phase diagram. ................................................................................ 34
Figure 12: SEM micrographs of the nanocrystalline diamond film (a) before heat
treatment, and after oxidation at 650ºC in the air for (b) 10 minutes and (c) 30 min. ... 37
Figure 13: Diamond crystals after heat treatment of 60 min at 1200 °C with the presence
of graphite points. ........................................................................................................... 38
Figure 14: Pull-outs in a mixed grain structure of diamond and cBN. ........................ 40
Figure 15: Thermal cracks in a diamond particle treated at 1000 ºC for 30 minutes in air
atmosphere. ..................................................................................................................... 41
Figure 16: Ellingham diagram for carbides. (a) first and (b) second transition series .. 46
Figure 17: Flowchart of the activities developed in the experimental procedure. ........ 48
Figure 18: (a) Scanning Electron Microscopy and (b) Confocal Microscopy of the
diamond powder used in this work. ................................................................................ 49
Figure 19: XRD of the initial diamond powder............................................................. 50
Figure 20: Particle size distribution of polycrystalline diamond powder. .................... 50
Figure 21: Micrographs of tantalum powder. ................................................................ 51
Figure 22: XRD of the tantalum powder. ...................................................................... 51
Figure 23: Particle size distribution of tantalum powder. ............................................. 52
Figure 24: Representation of the sample holder used. (a) Mold, caps, and support used
to encapsulate the powder and (b) capsule set ready for HPHT sintering. ..................... 53
Figure 25: High-pressure device used in the HPHT sintering....................................... 54
Figure 26: HPHT sintering press furnace. ..................................................................... 54

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Figure 27: Schematic configuration of pin-on-disc apparatus. ..................................... 56

Figure 28: SEM micrography of AISI 4340 steel surface used on the pin-on-disc tests.
........................................................................................................................................ 57
Figure 29: XRD of AISI 4340 steel used on the pin-on-disc tests. ............................... 58
Figure 30: SEM micrography of granite surface used on the pin-on-disc tests ............ 58
Figure 31: XRD of granite discs used on the pin-on-disc tests. .................................... 59
Figure 32: Confocal Microscopy of the diamond and (a) 2.5, (b) 5.0, (c) 7.5, (d) 10.0 wt.
% Ta mixtures. ................................................................................................................ 61
Figure 33: X-Ray Diffraction of powder mixtures. ....................................................... 62
Figure 34: EDS analysis of WC contamination on the PCD with 7.5 wt.% of Ta sample.
........................................................................................................................................ 63
Figure 35: Particle size distribution curves of powder mixtures. .................................. 65
Figure 36: Scanning Electron Microscopies of PCD with (a) 5.0 and (b) 7.5 wt.% Ta as-
sintered samples. ............................................................................................................. 66
Figure 37: X-Ray Diffraction of as-sintered samples. .................................................. 67
Figure 38: Fracture surfaces of the samples with (a) 2.5, (b) 5, (c) 7.5, (d) 10 wt. % Ta.
........................................................................................................................................ 69
Figure 39: Compressive strength and Young’s modulus of as-sintered composites. .... 70
Figure 40: Depth of penetration of PCD-Ta composites against SAE 4340 steel......... 71
Figure 41: Coefficient of Friction (CoF) of PCD-Ta composites tested against SAE 4340
steel. ................................................................................................................................ 72
Figure 42: Average Coefficient of Friction (CoF) of PCD-Ta composites against SAE
4340 steel. ....................................................................................................................... 73
Figure 43: Schematic illustration of tribological behavior at the third stage. ............... 74
Figure 44: Wear rate of 4340 steel after pin-on-disc test with PCD-Ta composites ..... 75
Figure 45: Wear rate of PCD-Ta composites after pin-on-disc test with 4340 steel. .... 76
Figure 46: Scanning Electron Micrographs of steel wear tracks after pin-on-disc with
PCD-(a) 2.5, (b) 5.0, (c) 7.5, (d) 10 wt.% Ta composites. ............................................. 77
Figure 47: SEM of the intern worn surfaces of 4340 steel discs tested against PDC-(a)
2.5, (b) 5.0, (c) 7.5, (d) 10 wt.% Ta composites. ............................................................ 78
Figure 48: EDS analysis of 4340 steel surface tested against PCD-2.5Ta composite. . 79
Figure 49: EDS analysis of PCD-5.0Ta pin surface tested against 4340 steel. ............. 79
Figure 50: Depth of penetration of PCD-Ta composites tested against granite discs. .. 80
Figure 51: Coefficient of Friction (CoF) of PCD-Ta composites tested against granite
discs. ............................................................................................................................... 81
Figure 52: Average Coefficient of Friction (CoF) at steady state of PCD-Ta composites
tested against granite. ..................................................................................................... 82

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Figure 53: Wear rate of granite after pin-on-disc test with PCD-Ta composites .......... 84
Figure 54: Wear rate of PCD-Ta composites tested against granite. ............................ 84
Figure 55: SEM of the worn surfaces of granite discs tested against PDC-(a) 2.5, (b) 5.0,
(c) 7.5, (d) 10 wt.% Ta composites. ............................................................................... 85
Figure 56: EDS analysis of granite surface tested against PCD-2.5Ta composite........ 86
Figure 57: EDS analysis of PCD-7.5Ta pin surface tested against granite disc............ 87

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LIST OF TABLES
Table 1: Main properties of diamond and graphite. ...................................................... 28

Table 2: Properties of the main materials used in the manufacture of cutting tools. .... 33
Table 3: Classification of some transition metals according to their reactivity with
carbon. ............................................................................................................................ 40
Table 4: Main properties of tantalum and its compounds. ............................................ 44
Table 5: Coefficient of thermal expansion of the main PCD binders. .......................... 45
Table 6: Theoretical density of elements used in the present work. .............................. 55
Table 7: Chemical Composition of AISI 4340 steel used on the pin-on-disc tests. ...... 57
Table 8: Typical chemical composition of granite. ....................................................... 59
Table 9: WC content in powder mixtures. ..................................................................... 63
Table 10: Average particle size for each mixture composition after milling process. .. 64
Table 11: Density values for as-sintered samples of PCD with different tantalum
concentrations. ................................................................................................................ 68

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SUMMARY
ABSTRACT ..................................................................................................................... 9
RESUMO ....................................................................................................................... 10
LIST OF PUBLICATIONS ............................................................................................ 11
LIST OF ABREVIATIONS AND NOMENCLATURE ............................................... 12
LIST OF FIGURES ........................................................................................................ 14
LIST OF TABLES ......................................................................................................... 17
1. INTRODUCTION ...................................................................................................... 21
1.1 Main Goal ............................................................................................................. 23
1.1.1 Specific Goals ................................................................................................ 23
2. LITERATURE REVIEW ........................................................................................... 25
2.1 The Carbon ........................................................................................................... 25
2.1.1 The graphite.................................................................................................... 26
2.1.2 The diamond ................................................................................................... 27
2.2 PCD and diamond tools ........................................................................................ 29
2.3 PCD manufacturing processes .............................................................................. 33
2.3.1 CVD ............................................................................................................... 34
2.3.2 Chock wave .................................................................................................... 34
2.3.3 HPHT process ................................................................................................ 35
2.4 PCD degradation processes .................................................................................. 35
2.4.1 Oxidation ........................................................................................................ 35
2.4.2 Graphitization ................................................................................................. 37
2.5 PCD binders .......................................................................................................... 39
2.6 Tantalum ............................................................................................................... 43
2.6.1 Tantalum as a PCD binder ............................................................................. 45
3. EXPERIMENTAL PROCEDURE ............................................................................. 48
3.1 Starting materials .................................................................................................. 49
3.2. Mixtures preparation ............................................................................................ 52
3.3 HPHT Process ....................................................................................................... 53
3.4. Density measurement ........................................................................................... 55
3.5. Diametral compression test .................................................................................. 55
3.6. Wear test .............................................................................................................. 56
4. RESULTS AND DISCUSSION ................................................................................. 61
4.1. Analysis of the powder mixtures ......................................................................... 61

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4.1.1 Effect of milling on powder homogenization ................................................ 61

4.1.2. Chemical analysis of mixtures ...................................................................... 62
4.1.3. Particle size distribution ................................................................................ 64
4.2. Sintered samples analysis .................................................................................... 65
4.2.1. Chemical Analysis......................................................................................... 66
4.2.2. Porosity Test.................................................................................................. 68
4.3. Mechanical behavior and fracture analysis .......................................................... 68
4.4. Tribological analysis ............................................................................................ 71
4.4.1. PCD-Ta system against 4340 steel ................................................................ 71
4.4.2. PCD-Ta system against granite ..................................................................... 80
5. CONCLUSIONS ........................................................................................................ 89
REFERENCES ............................................................................................................... 91

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Chapter 1:
Introduction

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1. INTRODUCTION
The manufacturing industry plays an indispensable role within the global

economy. However, this sector still demands urgent solutions in several operations due
to the large consumption of energy and resources. Previous data indicated that 31% of
total electricity consumption in the U.S. is held by the industrial sector. Within this, 75-
80% is occupied by machine tools in manufacturing processes. Part of the problem lies
in the inefficiency of current cutting tools, which demands many resources to operate
cutting and drilling processes. Furthermore, other difficulties such as the need for
cooling/lubrication strategies to reduce thermal losses from systems, have worried
scientists due to the environmental impact of cooling fluids. (DUFLOU et al., 2012)
(ZHOU et al., 2016), (PERVAIZ et al., 2020)
In this context, the research and development of novel cutting tools, as well as the
improvement of the existing ones, have been growing greatly in recent years. Several
materials have found a use for this purpose, and among the special tools, the diamond
tools, especially those made of PCD, stand out. (SZUTKOWSKA et al., 2015), (LI et al.,
2020)
Polycrystalline diamond (PCD) is an advanced material known for its unique

properties such as high hardness, excellent abrasion resistance, and elevated thermal
conductivity. Due to these characteristics, this material is widely used for cutting,
grinding, drilling, and polishing hard materials, such as stone, concrete, cemented
carbides, optical glass, advanced ceramics, and other difficult-to-process materials. (LI et
al., 2017a), (ARTINI et al., 2012), (BERGS et al., 2020), (NEVES, 2017), (LONG et al.,
2018)
Frequently, PCD is described as a composite of micron-sized diamond grains

bonded together in the presence of a metallic catalyst using high-pressures (5.5–8.0 GPa)
and high-temperatures (1450–1750 °C). The main function of the metallic binder is to
promote the union between the diamond particles by creating a network of bridges and
connecting neighboring grains. Moreover, using a binder can also offer benefits such as
reducing sintering pressure, improving mechanical performance, and inhibiting or
reducing degradation processes. Currently, the main materials used for this purpose are
Co, Fe, Ni, Cu, Ti, and Si. (CHEN et al., 2020), (WESTRAADT et al., 2015),
(VHARETA et al., 2020), (ROSA et al., 2015), (ZHANG et al., 2020)

22
However, some of these binders such as Fe, Ni, and Co are catalysts of
graphitization. Graphitization is a process found in carbonaceous materials when carbon
undergoes a transition from diamond to graphite. This degradation is very harmful
because the formed product has properties different from the diamond, damaging the
tool’s performance. (CHUANG et al., 2018), (SUN et al., 2016), (LIU et al., 2017a).
Due to the problems encountered by conventional binders, researchers have

attempted to develop or propose novel binders that can be applied to minimize such
difficulties. The research developed by Gurgel et al. (2020), Barreto et al. (2020), and
Mashhadikarimi et. al. (2020) demonstrated great potential in the use of niobium as a
PCD binder. This element reduced the occurrence of cleavage for intergranular fractures,
increasing the strength of the matrix, and promoted a reduction in the effects of
graphitization through the formation of niobium carbides, such as NbC and NbC0.84.
With properties similar to those of niobium, tantalum has been receiving

significant use in several applications as a pure metal, oxide, or carbide, and for this
reason, it is widely utilized in industrial, aerospace, medicinal, nuclear, and electronics
sectors. This metal shows attractive properties as chemical inertness, low reactivity,
excellent ductility, high melting point, high capacitance, and excellent conduction of heat
and electricity. Tantalum carbide (TaC) is a very hard refractory material and has
demonstrated a notorious high performance in cutting tools. (FILELLA, 2017), (SOUSA
et al., 2013), (CARVAJAL-CAMPOS et al., 2019)
Tantalum also has a coefficient of linear thermal expansion (CoTE) (6.5 × 10−6
K−1) closest to diamond (1.0 × 10−6 K−1) when compared to other conventional binders,
such as cobalt (13 × 10−6 K−1), iron (11.8 × 10−6 K−1), and nickel (13.4 × 10−6 K−1)
(CVERNA, 2002). These high differences can generate internal thermal cracks both
during the manufacturing process and the operational life cycle, which may significantly
reduce the tool's durability (ZHAO; DUAN, 2018), so employing Ta in this application
can help to minimize these issues. However, until the present moment, there were no
reports relating to its use as a PCD binder.

23
1.1 Main Goal
This work aims to study the applicability of tantalum as a novel polycrystalline

diamond agent binder, manufactured by powder metallurgy and High Pressure-High
Temperature (HPHT) processing, targeting applications in drilling and cutting industries.
1.1.1 Specific Goals
a) Investigate the effect of high energy milling on the mixture of diamond and
tantalum powders, the morphological modifications, reactivity, and possible
contamination during the process;
b) Analyze the densifications and integrity of the products after HPHT processing,
and the occurrence of phase formation and degradation processes;
c) Verify the influence of the binder amount on the mechanical and physical
properties, and the fracture mechanisms of as-sintered products.
d) Study the tribological behavior of PCD-Ta system on ferrous and ceramic

materials, involving the understanding of wear mechanisms and tribological properties,
to simulate applications in real situations of friction and wear.

24
Chapter 2:
Literature Review

25
2. LITERATURE REVIEW
2.1 The Carbon
The name carbon comes from the Latin word carbo, which means coal. It is
believed that the first description of this element occurred around 1780, but its use by
humans comes from prehistory. It is the sixth element of the periodic table, is found
abundantly throughout the planet Earth, from the surface to the nucleus, according to
evidence suggests. (NASIR et al., 2018), (MARTY; ALEXANDER; RAYMOND, 2013)
This element is fundamental for the composition of all organic forms existing in
nature, which turn it an essential material for the life on this planet. This component is
part of the composition of all living beings, being present in about 95% of chemical
compounds, in the atmosphere, in the oceans, soil, sedimentary rocks, and in fossil fuels.
Combined with oxygen atoms, it forms carbon dioxide (CO2), which is essential for the
processes of photosynthesis in plants. On the other hand, its combination with hydrogen
allows the creation of hydrocarbons, basic elements for important sources of energy, such
as oil and natural gas. (LIMA, 2012), (FALCAO; WUDL, 2007)
The carbon atom has an atomic number six (Z = 6), with an electronic
configuration of the type (1s2) (2s22px2py), and for an energetically stable situation needs
to be in the hybridized state. In a covalent network, each carbon atom can have one of
three hybridization states: sp3 (tetrahedral), sp2 (trigonal), or sp (linear). The result of
these interactions allows the occurrence of various allotropic structures of this compound,
in which the diamond, graphite, fullerenes, nanotubes, polymers, graphene, nanoribbons,
among others, stand out. (LIMA, 2012), (OGANOV et al., 2013), (MCENANEY, 1999),
(CABRAL, 2009)

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Figure 1: Some carbon allotropes: (a) Diamond, (b) graphite, (c) lonsdaleite, Fullerenes: (d) C 60
(buckyball), (e) C540, (f) C70, (g) amorphous carbon, (h) single-walled carbon nanotube. Source: Martinez-
Duarte et al. (2010)
2.1.1 The graphite
The origin of the word graphite comes from the Greek graphein, which means "to
write". In fact, graphite has been used to write since the beginning of history. It is believed
that the first pencils were made in England in the 15th century. This material was named
by Abraham Gottlob Werner in 1789 and consists of carbon atoms connected in huge flat
networks stacked on top of each other. (NASIR et al., 2018), (PIERSON, 1993)
This carbon allotrope is an excellent electrical conductor, which is why it is

convenient to be used in several electrical applications, such as electrodes for electric arc
furnaces and acting as a cathode in zinc-carbon batteries. This capacity derives from the
displacement of π electrons, a phenomenon that is not viable in diamonds due to the
restricted movement of electrons in its network arrangement. (LIMA, 2012), (NASIR et
al., 2018)
The crystalline structure of graphite is formed by several layers, in which the

carbon atoms are arranged to form a kind of “hive”, as expressed in Figure 2. Such atoms
are united by covalent bonds, with a distance in the basal plane of 1.42 Å, and a sp2
hybridization. This interatomic configuration is the trigonal type, and the electronic
clouds of the valence shell form an angle of 120º to each other. The interplanar distance

27
between two consecutive layers (or sheets) of graphite along the c-axis is 3.354 Å, more
than twice as long as the C-C connection distance, with weak interplanar forces of the
Van der Waals type. (CABRAL, 2009), (MCENANEY, 1999)
Figure 2: The atomic structure of graphite. The dashed lines indicate secondary forces between the
graphite planes. Source: Brehob et al. (2003)
2.1.2 The diamond
Just like graphite, diamonds have been known since ancient times. However, its
use was limited mainly to decorative props of the time. Nowadays, however, this material
finds applications in the most diverse fields of technology, operating in heat sinks,
semiconductors, cutting and wear tools, optical components, among others (NASIR et al.,
2018)
Diamond can be obtained naturally from deep layers of the Earth's mantle, under
high pressure and high temperature for hundreds of thousands of years, or by a synthetic
way from carbonaceous compounds, such as graphite, through thermal, chemical and/or
mechanical processes that provide similar thermodynamic conditions, but for shorter
times. (DOBRZHINETSKAYA, 2012), (KHMELNITSKY; GIPPIUS, 2014)
The crystalline structure of the diamond, shown in Figure 3, is too distinct from
its allotrope, graphite. It belongs to the cubic system (space group Fd3m), where each
carbon atom is covalently linked to four other carbon atoms, located at the vertices of a
regular tetrahedron, at 109.28º angles. The atomic distance is the same in all dimensions
(a = 3.24 Å), and its hybridization is sp3 type. Such a configuration makes it difficult to
move π electrons, resulting in a structure that does not conduct electricity. This difficulty
and the presence of strong C-C bonds promotes the high hardness of this material.

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(DRESSELHAUS, 1997), (CABRAL, 2009), (CHAGAS, V. M.; FILGUEIRA, 2012),

(DOBRZHINETSKAYA, 2012)
Figure 3: The atomic structure of the diamond. Source: Cabral (2009)
Table 1 indicates the main differences between the properties of diamond and
graphite. Since their structures are very different, it is expected that their properties are
also not similar.
Table 1: Main properties of diamond and graphite.
Properties Diamond Graphite
Crystalline structure Cubic Hexagonal
Hybridization sp3 sp2
Density (g/cm3) 3.51 2.27
Mohs hardness 10 ~1
Heat capacity (J.mol-1 K-1) 6.155 8.517
Thermal Conductivity (W m-1 K-1) ~2200 150
Resistivity (Ω) ~1012 ~3.10-3 – 4.10-6
Band gap (eV) 5,57 -0,04
Melting Point (K) 4450 4500
More intense Raman peak (cm-1) 1332 1582

Source: Cabral (2009), Moseley et al. (2018)
The differences between both chemical structures comes from their obtaining
processes: the diamond needs high pressures and high temperatures to be formed, and is
a metastable phase in atmospheric conditions. According to Le Chatelier's principle, the

29
diamond structure is formed to reduce the effects of the compressive force application
within the structure, which favoring a compact organization. (ABREU, 2001);
(KHMELNITSKY; GIPPIUS, 2014)
Still, this material has a high chemical inertness, does not react with common acids
at low temperatures, has a high value as a precious gem, and it is the hardest known
substance (with a hardness of 10 on the Mohs hardness scale), which is why is widely
used as abrasive material and in cutting and drilling tools. However, diamond also shows
disadvantages, as elevate brittleness. (MOREIRA, 2013), (AFONSO, 2018), (FALCAO;
WUDL, 2007)
2.2 PCD and diamond tools
During the last decades, the materials used for cutting tools have gone through a
wide development path. Nowadays, a machining operation can be performed in about 1%
of the time needed in the early 20th century. This is due to the growing improvements in
several aspects, such as the creation of anti-vibration tools, internal lubrication,
modification of conventional geometries, new coatings, and the development of special
tools. Among the special tools, diamond tools stand out, especially those made of PCD.
(NEVES, 2017)
Polycrystalline diamond or PCD is a composite made from diamond particles

combined with a metal binder through the sintering process. Due to its extreme hardness,
it is widely used as an abrasive element and in grinding and cutting tools for the
processing of hard materials such as concrete, cemented carbides, or natural stones.
(ARTINI et al., 2012), (NEVES, 2017)
There is also a growing interest in the use of PCD in the electro-electronic

industry, whose attraction lies in the properties of this material, such as high thermal
conductivity and low electrical conductivity. Several types of research have been
developed proposing its use in electrical superconductivity, optical windows,
microelectromechanical systems (MEMS), surface acoustic wave devices (SAW),
detectors, electrochemical electrodes, and electron emitters. (LI et al., 2018), (MAY,
1995), (ISBERG et al., 2004), (DENEUVILLE, 2000). Figures 4 and 5 indicates some of
these applications.

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Figure 4: Diamond crystal for optical applications. Source: Applied Diamond (2020)
Figure 5: PCD for detector device, manufactured by CVD. Source: Applied Diamond (2020)
Often, polycrystalline diamond has been associated with PDC (Polycrystalline

Diamond Compact) or TSP (Thermally Stable Polycrystalline Diamond Composite,
sometimes represented as TSDC). Such nomenclatures refer to Metallic Matrix
Composites (MMC), consisting of a PCD layer, a base or substrate matrix, and an
intermediate layer responsible for the union between the other two, illustrated in Figure
6. (BOLAND; LI, 2010), (MASHHADIKARIMI, 2017)
PDC tools are used in the civil construction industry and for cutting rocks, asphalt
and reinforced concrete, for prospecting natural stone quarries and large-scale
manufacture of various types of coatings. They are also used in the renovation of road
pavements, airport runways, modernization of metallurgical plants, nuclear plants,
bridges, and other structures. Also, PDC drills have been responsible for about 75% of
the tools used in oil drilling activities. (LIU et al., 2017b), (SCOTT, 2006). Figures 7, 8,
and 9 also indicate some of the PCD applications.

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Figure 6: Representation of a Polycrystalline Diamond Compact tool. Adapted from Mashhadikarimi

(2020).
Figure 7: Lapidary Diamond Core Drill Bits. Source: Gunther Diamond Tools (2020)
Figure 8: Inserts of polycrystalline diamond. Source: Applied Diamond (2020)

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Figure 9: PDC Drill Bits. Adapted from Rockpecker (2020) and DiamondWK (2020)
The main advantage of using the PDC is the increased toughness provided by the
base matrix, which absorbs the impact energy suffered by the diamond layer during
operation, thus ensuring an increase in the limit of mechanical resistance and its useful
life. The middle layer plays an equally important role as the other two, acting as the main
binding medium between them and transporting the energy absorbed by the PCD to the
substrate. Generally, the choice of the matrix is a decisive factor in the manufacture of
the tool, depending directly on the abrasiveness of the material to be cut or polished and
must meet several requirements, such as good chemical compatibility and mechanical
bond with the diamond, high hardness, and resistance, to resist to the abrasive work and
the wear speed. The most common matrices on the market are hard metal (WC-Co) and
Si3N4. (ARTINI et al., 2012), (BELNAP; GRIFFO, 2004), (FILGUEIRA; PINATTI,
2003), (MASHHADIKARIMI et al., 2016)
The biggest challenge found today in the development of cutting tools is the
junction of hardness and toughness. This issue derives from the fact that these properties
are inversely proportional, where the increase in one usually results in decreasing the
other. Figure 10 indicates the position of the main cutting tools in this balance, while
Table 2 shows a comparison between the main properties of these materials. It is believed
that the ideal tool material should have the hardness of the diamond, the chemical inertia
of alumina, and the toughness of high-speed steels. (GONÇALVES, 2008), (GRZESIK,
2017)

33
Figure 10: Hardness versus toughness for some conventional cutting tool materials. Source: Hosseini;
Kishawy (2014)
Table 2: Properties of the main materials used in the manufacture of cutting tools.
Thermal
Transverse Thermal
Hardness Expansion
Material rupture conductivity
(HV 10/30) Coefficient
strength (MPa) (W/m.K)
(µm/mºC)
High-speed
700 – 900 2500 – 4000 9 – 12 15 – 48
Steel
Carbides 1200 – 1800 1300 – 3200 4.6 – 7.5 20 – 80
Si3N4 1350 – 1600 600 – 900 3 – 3.3 20 – 35
Al2O3 1540 – 2100 400 – 800 5.5 – 8 10 – 38
CBN 3500 – 4000 500 – 800 4.9 100
PDC 5000 – 6000 600 – 1100 1.0 550

Source: Gonçalvez (2008)
2.3 PCD manufacturing processes
PCD manufacturing processes occur at temperatures and pressures favorable to

the growth of diamond phases. Such regions can be seen in Figure 11, which indicates
the main methods used to manufacture this material, such as HPHT (High Pressure - High
Temperature), CVD (Chemical Vapor Deposition), chock wave synthesis, and its
thermodynamically favorable conditions.

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Figure 11: Carbon phase diagram. Source: Dobrzhinetskaya (2012)
2.3.1 CVD
Chemical Vapor Deposition (CVD) is a technique used for the manufacture of

polycrystalline diamond films whose main applications include coatings of cutting or
abrasive tools, heat sinks, and other substrates for electronic circuits. This technique is
based on chemical reactions in the gas phase, inside a reaction chamber, which forms a
film of the desired material on a substrate. (CHANG et al., 2003), (ZHAO et al., 2019)
The CVD process begins with the insertion of precursor gases, usually methane
(or other carbon sources) and hydrogen, from the reactor chamber. The gases are then
thermally activated by hot-filament, plasma (DC, RF, or microwave) or combustion
flame. During activation, molecular hydrogen dissociates into atomic hydrogen. It acts
by decomposing the hydrocarbon to form a methyl radical, the precursor of the diamond.
The chemical species are then transported by convection or diffusion to the substrate,
where they are deposited, and the diamond film is nucleated, and it grows later. (MAY,
1995), (CHANG et al., 2003), (ZHAO et al., 2019), (CONTIN, 2014)
2.3.2 Chock wave
The shock wave synthesis is a technique used to manufacture nanodiamonds, also

known as DND (detonation nanodiamonds), from the detonation of carbon-based

35
explosives. The process takes place in a cooled stainless-steel chamber in the absence of
oxygen, and the most widely used explosives consist of mixtures of trinitrotoluene (TNT),
hexogen, and/or octogen. The explosion lasts around 0.3 μs, creating an environment of
very high pressures and temperatures inside the chamber, generating diamond crystals
with an average size of approximately 5 nm. After the process, a rigorous cleaning is
usually carried out to remove blasting soot, sp2 carbon, and metallic impurities, with the
aid of gaseous ozone or a nitric acid solution. This technique enables the industrial
production of large quantities of diamonds and is widely used. (CHANDRAN, 2019),
(DENG; MOLIAN, 2012)
2.3.3 HPHT process
The HPHT process is based on an attempt to simulate the natural conditions with
which the diamond originates in the depths of the Earth. In this technique, the graphite is
simultaneously submitted to a pressure above 6 GPa and heated at least above 1600ºC. A
metal catalyst such as Co, Fe, or Ni is generally used to assist the process. This technique
is one of the most used in the industry for the manufacturing of PDC tools and also in
micrometric crystals synthesis. (DOBRINETS et al., 2013), (SHENDEROVA; NUNN,
2017)
2.4 PCD degradation processes
Despite having high stability in standard ambient conditions, the increase in

temperature, an oxidant environment, and the presence of elements such as iron, nickel,
and cobalt, tend to cause some type of degradation in the PCD. Such modifications are
detrimental since the properties of its forming product are very different from those of
diamond, which compromises the performance of the piece (KHMELNITSKY;
GIPPIUS, 2014).
The most common diamond degradation processes include oxidation and

graphitization.
2.4.1 Oxidation
It is known that at low pressures, carbonaceous materials that exhibit both sp3 and
sp2 hybridization are subject to oxidation when exposed to oxygenated atmospheres at

36
elevated temperatures. Carbon reacts with oxygen and produces gaseous products CO and
CO2. (HOWE et al., 2001)
According to the work developed by Ogorodnik et al. (1985), diamond oxidation

usually starts at 773 K, decomposing according to the reaction below.
Cdiamond + O2 → 2CO + ∆T
Up to approximately 973 K, an endothermic reaction occurs with little or no CO

adsorption. Thus, the available oxygen is converted to partial carbon oxide or carbon
dioxide, and the reaction continues without diffusion limitation. Between 973 and 1273K,
adsorption processes begin, and there is an increase in the concentration of CO2 in
intergranular pores, which limits the diffusion of oxygen. At that time, the process is
governed according to:
Cdiamond + CO2 → 2CO + Camorphous + ∆T
At this stage, amorphous carbon sp3 is formed, which, with the continuation of the
reaction, is converted to amorphous carbon sp2. Finally, from 1273K onwards, there is an
increase in the CO2 layer, which inhibits diffusion and leads to a decrease in the oxidation
rate. With oxidation being hindered, graphitization then governs the process. (HOWE et
al., 2001)
Figure 12 indicates a nanocrystalline diamond film prepared by HFCVD (Hot

Filament Chemical Vapor Deposition) in the paper developed by Pu et al. (2010), before
and after oxidative heat treatment of 10 and 30 minutes at 650ºC. In the micrographs, it
is possible to observe the morphological modification of the structure due to the formation
of sp2 amorphous carbon.

37
Figure 12: SEM micrographs of the nanocrystalline diamond film (a) before heat treatment, and after
oxidation at 650ºC in the air for (b) 10 minutes and (c) 30 min. Source: Pu et al. (2010)
2.4.2 Graphitization
Graphitization is a process occurred in carbonaceous materials characterized by a

change from an sp3 to sp2 structure, in order to increase the thermodynamic stability of
the system. (CHUANG et al., 2018), (FEDOSEEV et al., 1986)
This transformation plays an important role in the sintering of polycrystalline

diamonds through HPHT processing. In this context, during the application of pressure
and temperature, the graphitization provides the formation of small points of graphite at
the interfaces of the diamond particles that grow with the progress of the process, acting
as a kind of bridge. After the appropriate time, these bridges are transformed into
diamonds, forming necks that unite the structure. (SILVA, 2016), (HOWES, 1962),
(SIDORENKO et al., 2013)
On the one hand, graphitization is essential for the diamond coalescence process.
On the other hand, it is also detrimental to the performance of PCD tools. This is because
graphite has very different properties than diamond, especially concerning its hardness,
which reduces the efficiency of this device (SUN et al., 2016), (ROSA, 2011),
(BUTENKO et al., 2000).

38
Under low pressures, the diamond-graphite transformation generally occurs at

appreciable rates only at temperatures above 1800 K. However, this process can be
catalyzed in ranges below 970 K when this compound is heated in an oxidizing
atmosphere or when it is in contact with certain metals transition, such as iron, nickel,
and cobalt. In addition, smaller particles tend to have a higher graphitization rate when
compared to larger ones due to their high surface energy. (QIAN et al., 2004), (ROSA,
2011), (BUTENKO et al., 2000)
The graphitization starts from the surface defects and spreads gradually with
increasing temperature. When propagated internally, this phenomenon can lead to
increased tension in the network and the creation of microcracks in the diamond, leading
to a decrease in tool life and cutting efficiency. (LI et al., 2012), (AFONSO, 2018)
Figure 13 presents a micrograph obtained in the work of Chagas and Filgueira

(2012), in which diamond crystals were subjected to a heat treatment for 60 min at
1200°C. Consequently, during the process, there was the formation of triangular
structures in compact planes of the {111} family, which characterize graphitization
points.
Figure 13: Diamond crystals after heat treatment of 60 min at 1200 °C with the presence of graphite
points. Source: Chagas, Filgueira (2012)
Various measures have been studied to avoid graphitization of diamonds,

including the application of protective coatings and the use of binders for controlling the
formation of hard phases. (ROSA et al., 2015), (ARTINI et al., 2012)

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2.5 PCD binders
The performance of PCD tools is directly related to their binding phase. This
phase is mainly responsible for the retention of diamonds within the piece. During the
manufacturing process, it must be able to bond the hard particles. During the tool's
operation, it must ensure that they remain firmly in position. The last function regards the
redistribution of the load within the diamond structure. (KIEBACK; SAUER, 2000),
(ROMANSKI et al., 2006)
The diamond-binder connection comes from physical, chemical, or mechanical

forces. The first one occurs through intermolecular forces, which include Van der Waals
forces and hydrogen bridges, and, although it is omnipresent in such structures, it is too
weak to allow good adhesion among those involved. The second one comes from metallic,
ionic, and covalent bonds, and its intensity depends on the types and number of bonds.
This type generally causes highest retention between the parts. However, it is only
obtained under certain conditions of pressure and temperature, and from chemical
reactions at the matrix interface during the sintering process. The existence of this
chemical reaction depends on the composition of the metal powder, the size and
distribution of the particles, the oxidation or reduction of gases, and the temperature and
duration of the sintering process. Lastly, the mechanical retention comes from the
mechanical interlocking between the matrix and the diamond grains, which are obtained
by adhesion or friction, where the diamond grains are compacted by the matrix through
contraction during cooling after sintering. Such tension arises from the differences
between the coefficients of thermal expansion of the two components, and it is
responsible for the mechanical retention capacity of the material. The efficiency of this
type of welding is related to the existing porosity, the thermal expansion coefficients, and
the mechanical properties of the matrix. (ZHAO; DUAN, 2018), (BOROWIECKA-
JAMROZEK; LACHOWSKI, 2017), (OLIVEIRA et al., 2015)
An ideal binder should essentially enable a good retention of the diamond in the
PCD piece. However, researchers have been also using binders to improve several other
points, such as the cutting capacity and physical integrity of the PCD, the reduction of the
pressure of sintering and the inhibition or reduction of degradation processes, such as
graphitization. (SUN et al., 2016)

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According to Artini et al. (2012), transition metals, such as nickel, iron, cobalt,
manganese, and titanium, are often used as PCD binders due to large vacancies in their d
orbitals. When in contact with the carbon, these orbitals react with the carbon p orbitals,
overlapping them and forming chemical bonds. Such reactivity provides a certain degree
of interaction between these elements, which may be low (no interaction), moderate (there
is a significant interaction), or with a tendency to form carbides. Table 3 shows some
transition metals and their type of interaction with carbon.
Table 3: Classification of some transition metals according to their reactivity with carbon.
Non-interacting Moderately
Period Carbide formers
metals interacting metals
4th Cu, Zn Co, Ni, Fe Cr, Mn, Ti, V
5th Ag Pd Y, Zr, Nb, Mo
6th Au, Hg - Hf, Ta, W

Source: Artini et al. (2012)
The binder quantity is also a parameter that requires a lot of attention during a
PCD tool manufacturing. A low amount of this component promotes low impregnation,
with a weak and inefficient diamond-diamond or diamond-substrate interface.
Consequently, such problem can be succeeded by an inadequate load distribution along
with the structure, inducing the occurrence of pull-outs (RAJMOHAN et al., 2012). An
example of a tool affected by pull-outs is shown in Figure 14, obtained from Loginov et
al. (2015) research, who developed a hybrid diamond and cBN cutting tool.
Figure 14: Pull-outs in a mixed grain structure of diamond and cBN. Source: Loginov et al. (2015)

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On the other hand, deleterious nanoprecipitates can be formed if the binder is

excessive. This happens because the coefficients of thermal expansion of these phases are
very different from the PCD one. With the thermal cycles resulting from the machining
work, such differences tend to provoke thermal stresses that may be sufficient to initiate
microcracks. Then, the microcracks damage the structure, affecting the toughness,
mechanical resistance, wear, and fatigue of the tool (MASHHADIKARIMI, 2017). Thus,
the binder quantity used on the industrial application usually ranges up to 15 wt.%. An
example of these thermal cracks can be seen in Figure 15, obtained in the work of Li et
al. (2009), in a diamond particle treated at 1000 ºC for 30 min in air atmosphere.
Figure 15: Thermal cracks in a diamond particle treated at 1000 ºC for 30 minutes in air atmosphere.
Source: Li et al. (2009)
Currently, most diamond tools use cobalt, iron, or nickel as a binding agent, since
they provide excellent chemical compatibility with the hard phase. However, these
elements are also catalysts for graphitization and other degradations, which, as previously
discussed, are harmful transformations to the tool. Besides, cobalt is toxic to its
manipulators and the environment. For this reason, researchers have been proposing new
solutions that can be applied to minimize such problems. (OLIVEIRA; FILGUEIRA,
2008), (LIU et al., 2017b)
Bovenkerk & Gigl (1978), through the patent US4224380A, proposed a chemical
method to remove cobalt from PCD using aqua regia, a concentrated mixture of nitric and
hydrochloric acid. Although the method has improved thermal stability, there has been a
decrease in wear resistance and fracture toughness of the pieces. Moreover, aqua regia is
a dangerous acid, and the risk to the operators is not minimized.

42
Other alternatives have been discussed and involves the application of new
binders, whether they are metallic or ceramic materials.
Chuang et al. (2018) reported the use of metallic titanium for thermal and
degradation protection of diamond tools. They obtained significant improvement results
thanks to the formation of superficial TiO2 film in the structure. The film consumed the
oxygen that would be destined for the formation of CO and CO2, protecting the PDC
against oxidation action.
Zhao et al. (2018) investigated a polycrystalline diamond made with 15% of a

binder composed of a mixture of Si, Ti, B, and Al (in a ratio of 80:10:5:5, respectively).
As a result, this novel binder increased the thermal stability of the PCD in an oxidizing
atmosphere, when compared to the conventional cobalt. Moreover, the authors study the
binder amount effect of SiC whiskers in the mechanical properties of the PCD. They
noticed a superior flexural strength of the samples, which was attributed mainly to the
formation of strong covalent bonds of diamond-SiC-diamond in the materials.
Akaishi et al. (1990) studied the thermal resistance of sintered diamonds with
small amounts of Co, Ni, or super invar alloy. The results showed notable graphitization
in Diamond-Ni samples after the thermal treatment. Also, cracking of as-sintered
compounds was dependent on the metal additive, where the Co additive resulted in the
lowest integrity pellet, compared to pellets with Ni alloy or super invar alloy.
Furthermore, cracking induced by heat treatment significantly was more frequent with
the increase of additive metal amount. This was explained by the difference among the
thermal expansion coefficients of the components.
Even the addition of another carbon allotrope, graphene, used in the work of Chen
et al. (2020), promoted an increase in electrical conductivity by about 42 times and 33%
of the wear resistance of conventional PDC.
The research developed by Gurgel et al. (2020) demonstrated great potential in

the use of niobium as a PCD binder. This element reduced the occurrence of cleavage for
intergranular fractures, increasing the strength of the matrix, and promoted a reduction in
the effects of graphitization through the formation of niobium carbides, such as NbC and
NbC0.84. Similarly, Masshadikarimi (2017) also found that niobium allows excellent
adhesion of the diamond to the PDC interface both during sintering and when using the

43
tool, and gave evidence of the absence of cracks, graphitization and possible separations
between the composite layers.
2.6 Tantalum
The discovery of tantalum happened in 1802 by the Swedish chemist Anders

Gustaf Ekeberg. The name tantalum arose from its oxide difficulty to be dissolved in acid.
Ekeberg then decided to allude to Greek mythology, where his namesake Tantalus, son
of Zeus, was condemned by the gods to starve and thirst near trees full of fruit and with
water up to the neck, but the elements moved away whenever they tried to reach them.
(SUNGAIL; ABID, 2020)
In 1809, the English chemist and physicist William Hyde Wollaston, during the
analysis of the oxides of columbite and tantalite ores, concluded that, although they have
different densities, they blocked oxides of the same element. Only in 1846, the German
Heinrich Rose determined that the columbite contained Ekberg's tantalum oxide and an
oxide of another chemical element, which he called niobium, alluding to the daughter of
Tantalum, from Greek mythology. (FILELLA, 2017), (SOUSA et al., 2013)
With atomic number 73, and belonging to group V of the periodic table, tantalum
is a silver-colored metal, ductile and highly resistant to corrosion. With a body-centered
cubic crystal structure, this refractory metal has one of the greatest melting points of the
periodic table, being able to form compounds with a wide variety of oxidation states,
ranging from +5 to -3, such as TaO, Ta2O5, TaC, Ta2C, and TaS2. At room temperature,
Ta does not react with air, water, or acids, except hydrofluoric or its mixture with nitric.
Under heating, Tantalum reacts with most non-metallic elements, generating products
that are often interstitial and non-stoichiometric. In addition, it is a material with high
capacitance and high thermal and electrical conductivity. (SOUSA et al., 2013)
Tantalum is a versatile material and can be used in several applications as a pure

metal, oxide, or through its alloys. For this reason, it is widely used in industrial,
aerospace, medicinal, nuclear, and electronics sectors. (SUNGAIL; ABID, 2020),
(LEVIN et al., 2019). Table 4 indicates some of the main properties of this metal.

44
Table 4: Main properties of tantalum and its compounds.
Property Value
Ta TaC
Atomic weight (g) 180.95 192.96
Density (g/cm3) 16.65 14.48
Melting Point (°C) 2996 3880
Vickers Hardness (MPa) 873 16700
Electrical resistivity at 20°C (µΩm) 12.4 25
Thermal conductivity (W/m K) ~ 57 ~28

Thermal expansion coefficient (10-6 K-1) 6.5 6.29
Young's modulus (GPa) 170-200 285-560
Source: Filella (2017), Rudolf (2016), Nino et al. (2015)
The main application of tantalum occurs from its oxide, Ta2O5, in the manufacture
of electronic components. It is estimated that 60% of all annual production of this element
is destined for capacitors manufacturing. However, this metal is also widely applied in
anti-reflective coatings for silicon solar cells, semiconductors, optical waveguides,
chemical and biological sensors, wave devices, and transistors. (NGUYEN; LEE, 2019),
(NETE; PURCELL, 2018)
Tantalum carbide (TaC) is a very hard refractory and has been used in high
temperatures applications, especially in high-performance cutting tools, rocket nozzles,
aerospace, and electronic propulsion systems, mainly due to its properties such as high
melting point, high hardness, and elastic modulus, high thermal and electrical
conductivity, and excellent resistance to chemical and thermal impact. (NINO et al.,
2015), (CARVAJAL-CAMPOS et al., 2019)
Moreover, tantalum alloys are used in cathodic protection systems for steel
structures in water towers and bridges, and in coatings for chemical process equipment,
such as tanks, valves, and heat exchangers. There are also reports of its use in prosthetic
devices (hip joints, cranial plates, screens for bone replacement, suture clips, etc.) due to
its excellent biocompatibility with the human body. (FILELLA, 2017), (SAGHERIAN;
CLARIDGE, 2019)

45
2.6.1 Tantalum as a PCD binder
Regarding the use of new binders for PCD, the works developed by Gurgel et al.
(2020), Barreto et al. (2020), and Mashhadikarimi (2017) indicate that niobium is an
excellent substitute for conventional binders. The primary sources of this material are
minerals, such as columbite-tantalite, with a formula (Fe, Mn)(Nb, Ta)2O6, from which
tantalum also comes. But the source it’s not the only thing in common for both elements.
Their physical and chemical properties are also strongly similar. (MA et al., 2020),
(BOSE; GUPTA, 2002)
Brazil and Australia are the global holders of the most abundant resources of
niobium and tantalum and, therefore, are the leading world producers of these metals,
followed by Canada, Mozambique, and Ethiopia. The demand for Nb and Ta in various
applications has steadily increased over the past two decades thanks to the production of
modern industrial materials and high-tech consumer products. (NETE; PURCELL, 2018),
(ZHU; CHENG, 2011)
The discovery of the use of niobium as a PCD binder also opened an opportunity
for an investigation centered at tantalum. And, although there are no records that indicate
its use as a polycrystalline diamond binder, this material is favorable for such application.
As can be seen in Table 5, there is an elevated difference between the thermal

expansion coefficients of the diamond and its conventional binders. The above
differences act creating thermal cracks that reduce the tool life under thermal cycles
exposition. Among the metals presented, Tantalum shows the closest thermal expansion
to diamond ones, which can help to reduce the mentioned problem.
Table 5: Coefficient of linear thermal expansion of the main PCD binders.
Compound Diamond Fe Co Ni Nb Ta
Thermal Expansion
1.0 11.8 13.0 13.4 7.3 6.5
Coefficient [ºK-1x10-6]
Source: Cverna (2002)
As stated by Lu et al. (2018), with the increase in temperature during the

machining processes, chemical reactions of carbide formation can occur between the
diamond and the active elements. Chagas et al. (2019) and Hashimoto et al. (2020)
indicate that such formations can assist with the protection against thermal damage of the

46
PCD, minimize degradative effects and assist in the machining processes. Therefore, it is
increasingly common the binder's application to reduce these transformations.
According to the Ellingham Diagram for carbides (Figure 16), tantalum has a
carbide formation facility superior to most other metals, such as chromium, vanadium,
and conventional PCD binders. The lower Gibbs free energy (ΔG) of phases like TaC and
Ta2C indicate high thermodynamic stability of such compounds. Thus, during possible
thermal transformations in the diamond structure, the remaining carbon that would be
transformed into graphite is destined for the formation of tantalum carbides. Unlike
graphite, which usually causes problems with cutting tools, carbides may assist in the
tribological and mechanical performance of diamond tools, since they are hard phases
and with good toughness.
Figure 16: Ellingham diagram for carbides. (a) first and (b) second transition series. Adapted from
Shatynski (1979).

47
Chapter 3:
Experimental Procedure

48
3. EXPERIMENTAL PROCEDURE
In this work, the development of polycrystalline diamond composites sintered

with tantalum binder was divided into three parts. The first one was dedicated to the
manufacturing of PCD-Ta mixtures. The second involved the HPHT sintering of the
mixtures obtained previously. Finally, the third part included the characterization and
testing of as-sintered composites. Figure 17 indicates the sequence of activities developed
in the project.
Figure 17: Flowchart of the activities developed in the experimental procedure.
According to the described flowchart above, analyzes and characterizations were

carried out at different moments of the work. The procedures included techniques such
as particle size distribution analysis, X-Ray Diffractometry (XRD), Scanning Electron
Microscopy (SEM), and Confocal Microscopy. These techniques were used to understand

49
the main phenomena of each stage. The main equipment and parameters used for these
characterizations are express below.
a) CILAS 1064 particle size analyzer, with particle size range between 0.04 and 500µm,
and in a water medium
b) X-ray diffractometer, Cu-Kα radiation, and Ni filter, with scanning from 20 to 140º
(2θ), a step of 0.02º, and speed of 3º/min.
c) Olympus LEXT Confocal Microscope - 3D Measuring L. Microscope DLS4000
d) Hitachi TM3000 Bench Scanning Electron Microscope, under vacuum.
3.1 Starting materials
Starting materials utilized in this study were powders of polycrystalline diamond

and metallic tantalum. The diamond powder was provided by HNHongxiang Superhard
Material Co. Figure 18, Figure 19, and Figure 20 show that this material presents uniform
morphology, with an average particle size of 43.32 µm. Furthermore, no contamination
was found in the XRD, which indicates the high purity of this powder.
(a) (b)
Figure 18: (a) Scanning Electron Microscopy and (b) Confocal Microscopy of the diamond powder used
in this work. Source: The author.

50
Figure 19: XRD of the initial diamond powder. Source: The author.
Figure 20: Particle size distribution of polycrystalline diamond powder. Source: The author.
The tantalum powder was supplied by Companhia Brasileira de Metalurgia e

Mineração (CBMM), with a purity of 99%, and an average particle size of 3.48 µm. The
low Ta diameter associated with the incidence of secondary forces, characteristics of this

51
element, results in a high incidence of agglomerates for this powder. Again, no

contamination was found in the XRD, which demonstrates the high purity of this material.
Figure 21: Micrographs of tantalum powder. Source: The author.
Figure 22: XRD of the tantalum powder. Source: The author.

52
Figure 23: Particle size distribution of tantalum powder. Source: The author.
3.2. Mixtures preparation
PCD-Ta mixtures were prepared with amounts of 2.5, 5.0, 7.5, and 10 wt.% of
binder, following the quantities conventionally used in the industry of up to 15%. Each
composition was homogenized in a Fritsch Pulverisette planetary ball mill, at the
Laboratory of Ceramic Materials and Special Metals (LMCME/UFRN), using hardmetal
vessel and balls. The high-energy milling was performed for 20 minutes, with a 10:1
ball/load ratio, at 300 rpm, in a wet medium of cyclohexane. These parameters were used
to provide homogenization of the powders without the occurrence of significant breaking
of the diamond particles. Moreover, high-energy milling was the chosen manufacturing
route as this process is capable to promote strong adherence of binder on PCD particles.
Then, the powders were dried in a muffle furnace at 90 ºC for 1h
The particle size distribution after mixing and the chemical composition were
examined by particle size analysis, Confocal Microscopy (CM), X-Ray Diffraction
(XRD), and Rietveld refinement.

53
3.3 HPHT Process
The mixtures made in the previous process were consolidated in the Laboratory of
Advanced Materials (LAMAV/UENF) using an HPHT device, which consists of a
press/furnace model DO138B, from Ryazantyashpressmash. For this, it was necessary to
manufacture a sample holder. The device consisted of a calcite capsule, which acts as a
compressive medium, and a graphite cylinder with caps, which act as conductive path
during the process.
The calcite capsules and graphite caps were manufactured by powders pressing, and
the graphite cylinders from cutting and machining sheets of this material. Figure 24
illustrates the three components used.
Figure 24: Representation of the sample holder used. (a) Mold, caps, and support used to encapsulate the
powder and (b) capsule set ready for HPHT sintering. Source: Mashhadikarimi (2017)
Then, the sets were assembled and the compositions were inserted into them. The
arrangements were taken to the press's HPD (High Pressure Device), where the samples
were subjected to a temperature of 1750 ° C and pressure of 7.7GPa for three cycles of 3
minutes each, resulting in 9 minutes for each sintering. Figures 25 and 26 indicate,
respectively, the arrangement of the set inside the HPD and the press/furnace used in the
process.
After the process, the set of calcite and graphite was destroyed, and the sintered
specimens undergo a chemical cleaning process to remove the common surface graphite
that may have resulted from the process. The cleaning consisted of immersing the samples
in water for 30 minutes in the ultrasound, followed by a bath in a solution of HNO3 and
HCl, in a proportion of 1: 3, for 20 minutes. Then, the composites were washed with
distilled water and dried in a muffle at 100 ºC for 1 hour.

54
Figure 25: High-pressure device used in the HPHT sintering. This device is composed of two anvils (1
and 2), supported by the multi-rings (3), and a calcite capsule (4). The blended powders are placed into
the (5) and the discs (6). During pressing is formed the compressive gasket (7). The heat is conducted to
the sample by a graphite cylinder heater (8). Adapted from Bobrovnitchii; Osipov; and Filgueira (2003)
Figure 26: HPHT sintering press furnace.

55
3.4. Density measurement
The density of the sintered samples was determined using the Archimedes
principle according to ASTM B962 (2013). A standard analytical balance with a precision
of ± 0,1mg was used to perform the weight measurements of the dry (md) and immersed
(mi) sample bodies. By using water as immersing medium with a density equal to d0
(0,997g/cm³ at 25 ºC), the experimental density of samples (d) was calculated according
to Equation 1.
𝑚𝑑
𝑑= 𝑑0 (Equation 1)
𝑚𝑑 −𝑚𝑖
Then, the relative density (dr) was determined through Equation 2, which
represents a relation between the density calculated by Archimedes principle and the
theoretical density samples (dt).
𝑑
𝑑𝑟 = . 100% (Equation 2)
𝑑𝑡
In this case, dt is the weighted average of the theoretical densities of used elements,
taking into account the percentage contents of each one by mass for each composition.
The theoretical densities of the elements involved in the calculations of the present work
are expressed in Table 6.
Table 6: Theoretical density of elements used in the present work.
Compound Diamond Ta
Theoretical Density (g/cm3) 3.51 16.68
3.5. Diametral compression test
A diametral compression test was carried out following the standards of ISO 4506,
for fragile materials. An Instron 5582 universal testing machine was used to fracture the
samples, with a load cell advance speed of 1mm/min. After the test, the products were
analyzed by SEM, to investigate the fracture mechanisms and understand other effects of
the binder in the inner area. Finally, the mechanical data were processed to obtain the
maximum stress and elastic modulus of the samples.

56
3.6. Wear test
The dry sliding wear tests were performed at the Study Group of Tribology and
Structural Integrity Laboratory (GET/UFRN) using a tribometer Magnum Engineers,
model TE-165LE, with a pin-on-disc geometry. The tests were conducted using pins of
the PCD-tantalum samples, and discs of granite and AISI 4340 alloy steel, in order to
simulate two common machining conditions that diamond tools are used for, involving
ceramic (rocky) and high-performance metallic materials. Figure 27 indicates the test
configuration used. In each analysis, the pins (composites) were kept fixed, and the disc
was rotated. The parameters used included a rotation speed of 500 rpm, which resulted in
a sliding distance of approximately 660 m, under an applied load (F) of 5 N, for a sliding
time of 10 minutes. Furthermore, the friction coefficient was recorded continuously
during the tests.
Figure 27: Schematic configuration of pin-on-disc apparatus. Source: Azevêdo et al. (2021)
The wear mass loss of the tribological pairs were quantified by weighing the
samples before and after the wear tests, using a digital scale Shimadzu (model:
AUW220D), with a precision of 0.1 mg. Here, the wear rate W was defined as the mass
quantity loss m divided by the applied load P and the wear distance d, as indicated by
Equation 3.

57
𝑚
W= (Equation 3)
𝑃.𝑑
The AISI 4340 steel discs used were cut by machining, and metallographically
prepared by sanding using silicon carbide abrasive papers with standard grit number of
#80-1200, following a polishing process with a diamond paste of 1 μm grit size. The steel
discs had dimensions of 30 mm (diameter) and 10 mm (height), Vickers Hardness of
338,2 ± 16,7 HV, and Roughness (Ra) of 0,068 ± 0,011 µm. On the other hand, the granite
discs had dimensions of 30 mm (diameter) and 10 mm (height), Vickers Hardness of
905,7 ± 37,3 HV, and Roughness (Ra) of 0,140 ± 0,032 µm. Table 7 and 8, and Figures
28–31 indicate, respectively, the chemical composition, the SEM, and XRD of these
materials.
Table 7: Chemical Composition of AISI 4340 steel used on the pin-on-disc tests.
Element Fe Ni Cr Mn C Mo Si S P
Content 95.1 - 1.65 - 0.70 - 0.60 - 0.38 - 0.20 - 0.15 -
0.04 0.04
(wt. %) 96.3 2.00 0.90 0.80 0.43 0.30 0.35
Source: ASM Handbook (1990)
Figure 28: SEM micrography of AISI 4340 steel surface used on the pin-on-disc tests. Source: The
author.

58
Figure 29: XRD of AISI 4340 steel used on the pin-on-disc tests. Source: The author.
Figure 30: SEM micrography of granite surface used on the pin-on-disc tests. Source: The author.

59
Table 8: Typical chemical composition of granite.
FeO +
Compound SiO2 Al2O3 K2 O Na2O CaO MgO TiO2
Fe2O3
Content 70.0 - 11.0 - 3.0 - 3.0 - 1.0 - 2.0 -
< 1.0 < 1.0
(wt. %) 77.0 13.0 5.0 5.0 2.0 3.0
Source: Reade Advanced Materials (2021)
Figure 31: XRD of granite discs used on the pin-on-disc tests.

60
Chapter 4:
Results and Discussion

61
4. RESULTS AND DISCUSSION
4.1. Analysis of the powder mixtures
4.1.1 Effect of milling on powder homogenization
The high-energy milling process can promote significant changes in the

morphology and particle size of the original powders. This effect of 20 minutes milling
on mixtures can be analyzed in Figure 32.
Figure 32: Confocal Microscopy of the diamond and (a) 2.5, (b) 5.0, (c) 7.5, (d) 10.0 wt. % Ta mixtures.
High incorporation and homogeneous distribution of the tantalum (dark phase) in

the diamond particles (bright phase) can be seen, even though the milling time was
relatively shorter than in previous works (JAWORSKA et al., 2017),
(MASHHADIKARIMI et al., 2020). According to Loginov et al. (2019) and Oliveira et

62
al. (2010), a good dispersion of binder impregnation is essential to promote strong

chemical bonds between the diamond particles during the sintering process, which will
assure good mechanical properties of the final products.
4.1.2. Chemical analysis of mixtures
According to the XRD of mixtures (Figure 33), no chemical reaction was detected
between the powders after the milling process, so the predominant bond between the two
components is relatively weak. Such behavior was also explained in the work of Lu et al.
(2018), who studied the mixture of diamond and copper by high energy milling. They
discussed that copper coats the diamond particles but does not diffuse and form carbide
with the hard phase during the milling. Therefore, the interaction between the components
is mainly Van der Waals's force. The lack of carbide or oxide formation supports the same
type of interaction in the current PCD-Ta system.
Figure 33: X-Ray Diffraction of powder mixtures.
The XRD of powder mixtures also indicates the presence of tungsten carbide
peaks. This phase may be related to the balls and milling vessel contamination, and its

63
content was measured by Rietveld refinement (Table 9). Figure 34 shows the distribution
of the element in the diamond with 7.5 wt. % Ta powder mixture via EDS analysis.
Table 9: WC content in powder mixtures.
Binder quantity (%) 2.5 5.0 7.5 10.0
WC contamination (%) 2.164 ± 0.025 1.064 ± 0.013 0.829 ± 0.013 0.541 ± 0.010
Figure 34: EDS analysis of WC contamination on the PCD with 7.5 wt.% of Ta sample.
The WC fragments were dispersed over the diamond particles, and most of them
ranged from 0.1 to 3 µm. The reduction of the contamination with increasing in the binder
content (Table 9) can be explained by two reasons. The first one is related to the
increasing of the tantalum’s concentration in the mixture. With the reduction of the
diamond percentage, there is fewer hard phase to wear out the vessels and balls. The
second reason involves the metal’s capacity to dissipate energy during the milling
process. According to Cunha et al. (2020) and Gurgel et al. (2020), metals with high
plasticity, such as copper, niobium, and tantalum, tend to deform during the milling
collisions. Thus, the metal dissipates the impact energy that could break the fragile phase
or increase the level of contamination. The work of Jaworska et al. (2017) justifies this
explanation using a ceramic as a PCD binder, under similar processing conditions used
in the present work. Studying a PCD with 10 wt. % of TiB2, they observed a WC
contamination of 7 wt. %, almost 13 times higher than with 10 wt. % of Ta.

64
4.1.3. Particle size distribution
Other phenomena noticed after the milling was the fracture of few diamond
particles and the decrease of average particle size (Table 10), although most of the original
ones have remained intact. These small cracks increase the particle's surface area, which
tends to improve the PCD-binder interaction.
Table 10: Average particle size for each mixture composition after milling process.
Binder quantity (%) 2.5 5.0 7.5 10.0
Particle size (µm) 43.33 41.09 39.94 38.12
Cunha et al. (2020) also observed a smaller reduction of the average particle size
after the milling of PCD with copper. It was justified that the high interaction between
the components happened due to the small fractures in the diamonds and to the high
plasticity of copper. Likewise, tantalum shows similar behavior due to its body-centered
cubic structure, resulting in an elevated number of slip systems. The high occurrence of
slip planes and directions enables the metal deformation, which allows it to spread and
embedded the diamond matrix during the milling (LIM et al., 2020; SHIELDS et al.,
1975; WHITEMAN et al., 2019).
According to the particle size distribution curves (Figure 35), all the powder
mixtures exhibit a unimodal behavior, however, there is a small flattening and slight
displacement to the left with the increasing of binder concentration. Lu et al. (2019),
Schubert et al. (2008) and Maurice et al. (1994) explain that during high energy milling
some of the fragile particles are fragmented by compressive and impact forces. Then, the
plastic phase acts as a binder and connects the brittle phase through relatively weak
bonding forces, such as the interlocking mechanical forces and Van der Waals. Finally,
the milling process allows the ductile-brittle compound to be formed by cold-welding
process.
The particle size distribution curves exhibited this behavior due to two active and
competitive phenomena. The first consists of some diamond particles rupture, which
causes a decrease of average particle size, dislocating the curve to the left.
Simultaneously, the binding particles embedded the PCD phase (Figure 32), increasing
its average diameter. Furthermore, despite most tantalum particles attached to the

65
diamond during the milling, there was some free fragment in the mixture, represented by
the passing volume between 3 and 15 µm. Both fixed and free fragments were
incorporated in the diamond interparticle voids during the HPHT process, as indicated by
the Scanning Electron Microscopies (Figure 36).
Figure 35: Particle size distribution curves of powder mixtures.
4.2. Sintered samples analysis
The general microstructure of the as-sintered composites is shown in Figure 36.

The micrographs indicate the Ta dispersion (white phase) between diamond grains (dark
phase). It possible to noticed that PCD particles didn’t change their original morphology
with the tantalum addition. Neither significant porosity nor grain growth is visible in the
micrographs after the sintering. This corroborates with the preview theory (VHARETA,
et al., 2020) that binder fills the interparticle voids, creating a network of bridges and
connecting neighboring grains during the HPHT process.

66
(a) (b)
(c) (d)
Figure 36: Scanning Electron Microscopies of as-sintered PCD with (a,c) 5.0 and (b) 7.5 wt.% Ta. (d)
Typical diamond graphitization morphology indicated by Chagas, Filgueira (2012).
4.2.1. Chemical Analysis
The XRD of as-sintered compositions (Figure 37) demonstrates that all samples
kept their diamond structure. Furthermore, the peaks related to WC contamination were
retained, which is a different phenomenon than the one studied in Jaworska et al. (2017)
work. In their research, a transformation of part of the WC in WB and W2C0.84 phases
was observed after the HPHT sintering, which was explained by a reaction between the
binder (TiB2) and the WC. On the other hand, in the present study, the lack of tungsten
carbide transformation can be related to its small quantity in all the samples and to the
low chemical reactivity to the formation of Ta-W compounds (WANG et al., 2017), that
preserves the original WC phase.
Another information presented by the X-Ray Diffraction concerns the graphite

peaks. As discussed in the work of Gurgel et al. (2020), this phase is probably more linked
to surface contamination from graphite mold tooling, than to graphitization phenomena.
Despite careful and meticulous post-sintering cleaning, such impurities could not be fully

67
removed, and remains in intergranular regions of the composites. Furthermore, the

sample's surface does not present a typical graphitization morphology (Figure 36-d),
which supports the hypothesis that the encountered graphite is a remain of mold tooling,
instead of being created by PCD degradation. In addition to the preview phases, Figure
37 indicated the conservation of metallic tantalum in all samples, however, TaC formation
was also identified.
Figure 37: X-Ray Diffraction of as-sintered samples.
According to Ellingham's Diagram for carbides (SHATYNSKI, 1979), tantalum

has a carbide formation facility superior to most metals, like Ti, Cr, V, and common PCD
binders. This happens due to the lower Gibbs free energy (ΔG) of phases like TaC and
Ta2C, which assure high thermodynamic stability for such compounds. In fact, carbide
formation can be a strategic manner to enhance the properties of PCD. As reported by Lu
et al. (2018b), this mechanism tends to improve the bonding strength between the phases
since the chemical combination is stronger than the physical one. Furthermore, authors
like Chagas et al. (2019), and Liu et al. (2017a) studied the formation of TiC and SiC,
respectively, to enhance the thermal stability of diamond composites. They explain that

68
carbide transformation consumes the free carbon that would become undesirable phases.
Thus, it is possible to prevent degradative effects in the structure, as graphitization.
4.2.2. Porosity Test
After the HPHT sintering, the specimen's densities were measured based on the
Archimedes principle. The density values of PCD-Ta compositions are exhibited in Table
11. According to the results, the as-sintered composites exhibit a densification ranging
between 94.0% and 97.5%, which are comparable to other studies involving PCD
sintering by HPHT technique (JIAN et al., 2020) (LV et al., 2019).
Increasing Ta quantity on the samples also reduced the theoretical densification.

This trend can be related to the lighter by-product formation on the as-sintered
composites, such as TaC. According to Nino et al. (2015) and Filella (2017), tantalum
carbide has a density of ~14.5 g/cm3, while metallic Ta has a density of ~16.7 g/cm3. As
indicated by the XRD (Figure 37), part of the metallic Ta on all composites was
transformed into TaC, which due to its lower density tends to decrease the composite's
theoretical density. As samples with a higher percentage of Ta tend to form more carbide,
it is reasonable that theoretical density undergoes an equivalent reduction. Consequently,
the densification values are affected.
Table 11: Density values for as-sintered samples of PCD with different tantalum concentrations.
Binder quantity (%) 2.5 5.0 7.5 10.0
Measured density (g/cm3) 3.49 3.53 3.56 3.58
Theoretical density (g/cm3) 3.58 3.65 3.73 3.81
Densification (%) 97.5 96.6 95.3 94.0
4.3. Mechanical behavior and fracture analysis
The variation of binder’s dispersion in the as-sintered bodies can be observed in

Figure 38, which shows the fracture surfaces of the samples after the diametral
compression test. It is possible to notice that the fracture surface was modified according
to the binder quantity. Samples with lower binder amounts showed more incidence of
cracks and particle separations, mainly due to the weaker interface caused by the lack of

69
metal in some regions. This leads to a predominance of fracture mechanisms related to

cleavage rather than transgranular ones. On the other hand, fractures were mostly
intergranular with the binder increasing, due to the reduction of these defects.
According to McNamara et al. (2015), the occurrence of transgranular fractures

instead of cleavage in diamond materials implies strengthened grain boundaries. This is
a consequence of a good contact between the particles that facilitated the carbon diffusion
during sintering. Additionally, strong intergranular bonds provide the increased driving
force required for crack deflection. Thus, it is more difficult to propagate such a defect
within the material, leading to an increase in mechanical strength. In Figure 39 it is
possible to see these effects on the mechanical properties of the samples.
Figure 38: Fracture surfaces of the samples with (a) 2.5, (b) 5, (c) 7.5, (d) 10 wt. % Ta.

70
Figure 39: Compressive strength and Young’s modulus of as-sintered composites.
The increase of the tantalum concentration provided a larger binder filling in the
interparticle spaces. This may be one of the reasons that explain the increase in
compressive strength with the increment of Ta percentage. According to Lammer (1988),
internal defects from poorly bound particles lead to a higher failure rate in diamond
materials. This idea corroborates with the mechanical results, which show that the
samples with a lower binder content had lower mechanical resistance. The increase in
Young's Modulus can also be justified by the increased filling of intergranular voids.
Werner et al. (1997) attribute the elastic modulus reduction to the presence of these voids,
which weaken the bonds between the diamond particles. Even so, according to data from
Sernicola (2018) the Young's Modulus values recorded in this work are comparable to
those already recorded in the literature.
Scott (2018) also explains that the thermal and elastic anisotropy between the two
phases can result in high interfacial tensions. These stresses allow the micro cracks to
propagate along the boundaries between the two components. Other factors such as
impurities, quantity, size and distribution of the second phase, degree of plastic
deformation, and fragmentation of diamond grains during synthesis can directly affect
fracture resistance. In general, the increase in the binder content contributed to the
increase in the integrity of the specimens in the present research.

71
4.4. Tribological analysis
The tribological tests were conducted aiming to analyze the applicability of the
PCD-Ta system with different concentrations of tantalum. The composites were tested in
wear conditions against ferrous (steel 4340) and ceramic (granite) materials. During the
experiments, the tribometer sensors provided information related to the wear of the
tribological pairs and friction coefficients close to the contact region of each pair.
4.4.1. PCD-Ta system against 4340 steel
a) Depth of penetration
According to the depth of penetration measures (Figure 40), all the compositions
exhibit intense wear rate in the first seconds of the test, followed by a steady-state,
characterized by a variation of the penetration rate almost imperceptible. Furthermore,
PCD with 2.5 wt.% Ta sample exhibited the severest wear, while the other compositions
followed a downward trend with increasing binder percentage. These phenomena can be
directly related to the PCD/Ta ratio of composites. Samples with lower Ta amount has
higher PCD percentage. Thus, as diamond is harder than tantalum, such compositions
tend to cause more significant wear on steel.
Figure 40: Depth of penetration of PCD-Ta composites against SAE 4340 steel

72
b) Coefficient of Friction
Figure 41 indicates the variation of the Coefficient of Friction for the tribological
pairs throughout the tests. Composites with the highest PCD percentages shown higher
values of CoF than samples with the lowest quantity. As previously discussed, this effect
is caused mainly by the elevated hardest phase amount in the samples, which tends to
result in a severest tribological wear. Moreover, it is possible to notice that all
compositions presented three different stages, which is mainly caused by the wear
mechanisms phenomena involved in each moment.
Figure 41: Coefficient of Friction (CoF) of PCD-Ta composites tested against SAE 4340 steel.
The first stage has taken place up to 50-60 seconds of the test. At this moment,
samples manifested the highest values and largest amplitudes of CoF, as registered in
Figure 42. This stage can be associated mainly with the "stick-slip" phenomenon.
According to Jackson and Morrell (2011), the stick-slip is a relaxation-oscillation
situation, developed in the dynamic contact between two surfaces. This mechanism is
described as surfaces alternating between sticking to each other and sliding over each
other, with a corresponding change in the force of friction, and consequently, in the CoF.

73
As indicated by Salguero et al. (2018) study, the large Coefficient of Friction

amplitude may be associated with the presence of small asperities that creates surface
roughness on initial materials. Such irregularities promote smaller superficial contact
between the tribological pair, resulting in higher contact pressures. Then, the action of
elevated contact pressures tends to promote detachment of wear debris from tribological
pair on the sliding track, favoring the system instability growing and increasing the
amplitude of CoF values. The combination of all these phenomena results in the
appearance of effects relating to abrasive wear mechanisms. Hence, this is the period that
occurs the greatest loss of mass in samples, as indicated by Figure 40.
Figure 42: Average Coefficient of Friction (CoF) of PCD-Ta composites against SAE 4340 steel.
The tribological pairs' temperature is also directly affected in the first stage. As
the wear intensity is more severe at this moment, the friction process increases the thermal
energy of the system, leading to a rapid temperature raising close to the pair contact area.
Therefore, the combination of friction and temperature favors adhesive phenomena
between the surfaces of the tribological pair, leading the system to the second stage.
The period of the second stage varied according to PCD-Ta composition, but
mostly occurred between 50-100s of the test. This stage was characterized by a decrease

74
in CoF values and by a trend of pairs temperature stabilization. This happened mainly due
to the formation of an adhesion layer of steel caused by the continuous sliding of the pin
over previously worn sections, also called stratified sections. Thanks to these conditions,
adhesion of wear debris over the slip track and pin surface induces the modification
towards softer topographies between contact elements, leading to a sliding process where
surfaces of the same material (film) contact each other. As a consequence, the system
reached the third stage.
Finally, the last stage, also known as “steady-state”, has started at ~100s of the
test. At this time, both CoF, wear, and temperature assumed a stability state due to the
growth of the adhesion layer of steel, as indicated by Figure 43.
Figure 43: Schematic illustration of tribological behavior at the third stage.
According to Zhang et al. (2020), the adhesion layer composition is also

influenced by the ambient air condition, which creates an absorbed film constituted by
water or oxygen molecules on the surface of tribological pairs. In a different ambient,
such as in high vacuum conditions, the pair tends to suffer severest wear effects because
spalling pits and adhesion appeared on PCD surface, caused by strong σ bonding between
pairs. At ambient air condition, on the other hand, absorbed film passivation of dangling

75
bonds isolates tribological surfaces, reducing the direct contact between the surfaces of
the friction pair.
c) Wear rate
The wear rate is an important parameter to be considered in the tribological

analysis, once it can predict the PCD performance and efficiency in cutting and drilling
applications. Figure 44 indicates the wear loss of 4340 steel after tribological tests against
PCD-Ta composites. The wear rate was significantly higher for steel discs submitted to
wear against PCD-Ta composites with lower binder quantity. In conformity with previous
analysis, the other compositions followed a downward trend with increasing binder
percentage. The last effect is a consequence of the decreasing of the hardest phase amount
in composite samples, which results in milder wear in the discs.
Figure 44: Wear rate of 4340 steel after pin-on-disc test with PCD-Ta composites
As indicate by Figure 45, all PCD-Ta samples undergo a mass loss during the
tribological experiment. Opposite to the disc’s behavior, samples with elevated binder
quantity exhibit a higher mass decrease than samples with lower Ta percentage. Such
phenomenon can be related to detachment soft phases presented in composites, like

76
graphite and metallic tantalum (Figure 37). Due to the action of applied load during
sliding, these phases tend to detach from interparticle regions of composite and can either
leave the sliding path or attach to adhesion film (Figure 43). Thus, samples with lower
percentage of phases different than PCD experienced less mass loss.
Figure 45: Wear rate of PCD-Ta composites after pin-on-disc test with 4340 steel.
d) Pair surface analysis
Figures 46 and 47 indicates the wear tracks on the steel discs after tribological
tests with PDC-Ta composites. As showed by depth of penetration curves (Figure 40),
samples with lower binder quantity provoked severer wear at steel surfaces, which
resulted in deeper scars on the sliding path (white regions). According to Figure 47,
grooves were produced at 4340 steel during the tests by all PCD-Ta composites,
evidencing the occurrence of abrasive wear mechanisms. Furthermore, is possible to
notice the appearance of the adhesive wear mechanism caused by the adherence of the
debris on steel surface.

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(a) (b)
)
(c) (d)
)
Figure 46: Scanning Electron Micrographs of steel wear tracks after pin-on-disc with PCD-(a) 2.5, (b)
5.0, (c) 7.5, (d) 10 wt.% Ta composites.
The EDS-SEM analysis (Figure 48) of worn surfaces indicates that the chemical
composition of debris was constituted mainly by Fe and carbon. As discussed at
Coefficient of Friction section, raising temperature caused by the friction process tends to
promote adherence of steel debris on the disc surface, which justifies the Fe composition.
On the other hand, the carbon fragments can be originated from small pieces of PCD
particles that may have detached from the as-sintered bodies, or from interparticle
graphite present on the surface of composites. The last explanation seems to be more
reasonable because graphite is a softer phase and does not are strongly bonded within the
composite, as PDC particles ones. Thus, graphite fragments are more likely to detach
from as-sintered bodies when the set is submitted to the wear process.

78
(a) (b)
Adhesive debris
Grooves
Grooves Adhesive debris
(c) (d) Adhesive debris
Adhesive debris
Grooves Grooves
Figure 47: SEM of the intern worn surfaces of 4340 steel discs tested against PDC-(a) 2.5, (b) 5.0, (c)
7.5, (d) 10 wt.% Ta composites.
Moreover, no traces of Ta were found on the steel surfaces. This result can be
directly related to the presence of stable TaC on as-sintered pins, formed during the HTHP
sintering process. The stable carbide forms a strong chemical bond with the diamond
grains, enhancing the bonding force between the phases. The presence of these bonds
makes it difficult for the diamond grains and TaC particles to initiate the phenomena of
micro-fracturing and detachment from pin bodies during the tribological test. Such
behavior was also observed in the work of Zhang et al. (2020), who noted the
improvement of PCD exfoliation resistance due to the formation of TiC phase.
On the other hand, EDS analysis of pins (Figure 49) exhibits the presence of steel
on its surface, indicating an adhesive interaction between both components. Transfer
films formed during sliding tests for diamond-related materials have been frequently
observed in previous studies (LI et al., 2017b), (SÁNCHEZ-LÓPEZ et al., 2003),
(SCHALL et al., 2010). As previously discussed in the present work, such phenomena
can be related to the interaction of the PCD surface with steel debris. These fragments

79
detached from the wear process, and by the thermal action of friction tends to adhere in
the PCD grains.
Figure 48: EDS analysis of 4340 steel surface tested against PCD-2.5Ta composite.
Figure 49: EDS analysis of PCD-5.0Ta pin surface tested against 4340 steel.

80
4.4.2. PCD-Ta system against granite
One of the current most crucial challenges to the granite/marble industry is to

achieve efficient and precise tools that can cut these materials. Such issues arise mainly
because just a few materials are hard and tough enough to cut through the granite, as PCD
ones do. Still, the development of PCD tools improvement is necessary to guarantee
longer operational life, minimization of costs, and wear reduction of such tools. The
results of PCD-Ta system performance against granite are express below.
a) Depth of penetration
The depth of penetration measures (Figure 50) indicates that samples with lower Ta
quantity provoked severer penetration on granite discs, following a downward trend with
increasing binder percentage. Similar to what happened on steel discs, all the
compositions exhibit an intense wear rate in the first seconds of the test, followed by a
steady-state, characterized by a small variation of the penetration rate. Furthermore, the
granite discs undergo a significantly smaller depth of penetration when compared to steel
ones. This happened because the granite hardness (~ 905 HV) is almost thrice than the
steel one (~ 340 HV). Thus, it is more difficult to wear out the pieces.
Figure 50: Depth of penetration of PCD-Ta composites tested against granite discs.

81
b) Coefficient of Friction
Comparing the different PCD-Ta compositions, it is possible to notice that the PCD-
Ta system tested against the granite discs shows similar characteristics to the steel tests,
such as the occurrence of three different tribological stages for all samples. Besides,
composites with the lowest Ta percentages exhibited higher values of CoF than samples
with the highest quantity (Figure 51). As previously discussed, this is due to the higher
percentage of the hard phase in the samples, which tends to produce severer wear on the
discs. However, despite some similarities, there are some distinctions between both
analyzes.
Figure 51: Coefficient of Friction (CoF) of PCD-Ta composites tested against granite discs.
The first difference is observed in the numerical values of the CoF. While steel pairs
exhibited a maximum CoF of ~ 0.87, granite pairs presented a maximum value of up to ~
0.50. Such phenomenon occurred mainly due to the higher hardness of granite when
compared to steel, which limits significantly the disc's wear. Consequently, the system
undergoes a lower depth of penetration and lower CoF values.
The stage durations have also remarkably changed. Unlike observed in pairs with
steel (in which the first stage lasted up to 50-60s), the first stage of granite was quite brief,
lasting up to ~13 seconds the test. At this moment, samples showed a rapid increase of

82
the CoF, reaching a maximum value of 0.50, 0.47, 0.42, and 0.38 to samples with 2.5,
5.0, 7.5, and 10.0 wt.% Ta, respectively. Shortly after, the values started to decline,
characterizing the second stage.
The second stage was noticeably longer to granite pairs, lasting up to ~100-150
seconds. One of the reasons that may explain the increase of second-stage duration is the
difficulty of forming adhesive films in ceramic materials, as granite. On steel pairs, the
film formation by the interaction between debris and composite materials is favored by
the high plasticity of the steel fragments associated with the metallic binder of the pins.
On the other hand, the granite debris is composed of hard phases with low plasticity,
which makes it difficult the adherence between the surfaces. Furthermore, the metallic
percentage of the composites directly affects these adhesive phenomena, which is why
samples with 7.5 and 10.0 wt.% Ta enters in the steady-state faster, while samples with
2.5 and 5.0 wt.% Ta spends more time in the second stage.
Figure 52: Average Coefficient of Friction (CoF) at steady state of PCD-Ta composites tested against
granite.
With the increase in the sliding time, all studied compositions entered the third stage
or steady-state, characterized by a CoF values stabilization. Even so, it is notable that the
CoF general amplitude was high for all samples (Figure 52), but more remarkable in those
with lower binder quantity. As explained in the work of Sha et al. (2016), this occurrence

83
is mainly related to the higher presence of fragile debris, detached from the sliding tracks
by the increase in contact pressure, which increases the system instability and,
consequently, the amplitude of CoF values. Samples with higher PCD content showed an
intensification of these phenomena since they tend to cause stronger disc wear.
c) Wear rate
Figure 53 exhibits the wear loss of granite discs after tribological tests against
PCD-Ta composites. Similar to what was observed in steel discs, the wear rate of granite
materials was significantly higher for steel discs tested against PCD-Ta composites with
a lower binder percentage. The other compositions followed a downward trend with
increasing Ta quantity. Again, this result is directly associate with the amount of hardest
phase in composite samples. Elevate PCD percentages produce intense wear on the
granite discs due to the more prominent difference of hardness between the materials.
Moreover, the wear rates of granite discs are comparable with previous studies (YAN et
al., 2016), (MENG et al., 2018), (MENG et al., 2019) involving diamond-related
materials.
On the other hand, all PCD-Ta pins also undergo mass loss during the pin-on-disc
test, as shown in Figure 54. Contrary to disc’s behavior, samples with elevated Ta
percentage exhibited a higher mass loss than samples with lower binder quantity. This
event can be related to the detachment of second soft phases from the composites, such
as graphite and metallic tantalum (Figure 37). During the sliding, these phases tend to
detach from interparticle regions of composites due to the action of applied load, and can
either leave the sliding path or attach to adhesion film (Figure 43). Thus, samples with a
higher percentage of these phases experienced further mass loss. Furthermore, both pins
and discs exhibit less wear rate on the granite tribological tests comparing to the steel.
This occurred because granite is harder than steel, which results in milder wear
phenomena when pairs are submitted to the same load.

84
Figure 53: Wear rate of granite after pin-on-disc test with PCD-Ta composites
Figure 54: Wear rate of PCD-Ta composites tested against granite.

85
d) Pair surface analysis
Figure 55 exhibit the wear tracks on granite discs surfaces after the tribological
tests with PDC-Ta composites. It is possible to notice that all discs undergo groove
formation, which is mainly caused by the occurrence of abrasive wear mechanisms with
the load application. As demonstrated by the depth of penetration curves (Figure 50),
tribological pairs with lower binder percentages produced severer wear at discs surfaces,
which resulted in deeper scars on the sliding path.
Figure 55: SEM of the worn surfaces of granite discs tested against PDC-(a) 2.5, (b) 5.0, (c) 7.5, (d) 10
wt.% Ta composites.
The SEM micrographs also show the presence of several debris, especially with
particular and flak morphology. The EDS analysis (Figure 56) indicates that the debris
was composed mainly of Al, Si, Na, Ca, Mg and K, demonstrating the own granite wear
predominance. Opposite to the steel behavior, granite debris shows a lower tendency to
form adhesive phenomena on the granite discs due to the ceramic nature of this material.
In general, ceramic materials show a higher chemical inertness than metals owing to the
predominance of covalent bonds on their structures. This characteristic results in an
elevated difficulty to form a ceramic-ceramic adhesion compound on granite discs, which

86
explains why PCD-Ta/granite system spends more time in the second stage during the
tribological test (Figure 51). Eventually, the successive action of wear (Figure 50) and
temperature results in the union of some granite fragments with the own disc, however
with a weaker bonding intensity than that observed in steel discs. Thus, although there
are adhesive wear mechanisms on PCD-Ta/granite pairs, it is much lower than the one
observed for steel pairs.
Figure 56: EDS analysis of granite surface tested against PCD-2.5Ta composite.

87
Another point observed on the granite worn surfaces is the presence of some
microcracks toward the sliding path. As indicate by the work of Johansson et al. (2019),
such defects are especially frequent in tribological wear of ceramic materials, like granite,
due to the fragility and high deformation difficulty of these compounds. In the present
study, cracks were more noticeable on tests with higher diamond content materials, which
can be justified by the greater wear intensity of these pairs. In addition, Erdemir & Martin
(2018) explains that in the case of brittle materials like ceramics, small surface edges can
cause micro-cracking under the influence of highly concentrated stresses and thus give
rise to material removal. Repeated sliding passes over the same contact area may also
trigger micro-fatigue events away from the contact spots and thus weaken the structure
and further accelerate the wear process.
EDS analysis of PCD-Ta pins (Figure 57) also indicates the presence of granite
fragments on the composite surfaces. As explained earlier, such adhesive phenomenon is
mainly related to the interaction of granite debris with the composite's metallic phase.
With the continuous thermal action of friction, the ceramic particles tend to form weak
bonds with pins, but with a lower intensity than that observed for steel pairs.
Figure 57: EDS analysis of PCD-7.5Ta pin surface tested against granite disc.

88
Chapter 5:
Conclusions

89
5. CONCLUSIONS
This work brings several novel concepts to the manufacturing industry by

investigated the viability of tantalum as an alternative binding agent for PCD sintering.
According to the analysis and outcomes discussed previously, the following conclusions
can be inferred from this research:
- After the high-energy milling, the tantalum powder embedded the diamond particles
through relatively weak forces, and no occurrence of chemical reactions between the two
compounds were observed.
- Some diamond particles were broken during the milling, but no significant change in
the particle size distribution was achieved. On the other hand, such fractures may have
improved the diamond-binder interaction due to the increase of the particle's surface area.
- Minor contaminations from the milling process were detected in the studied mixtures,
however, the tantalum acted significantly to reduce this occurrence by dissipating the
impact energy during the process.
- XRD indicates that the as-sintered samples kept their PCD structure. TaC resulting from
a reaction between the free carbon and the metallic Ta during the sintering process was
also identified.
- The predominance of the fracture mechanism was affected by the increase of Ta amount,
which reduced the cleavage occurrence on as-sintered bodies. This can be related to
higher metallic filling in the interparticle voids, strengthening the Di-Di bonds during the
sintering process.
- Tribological results reveal that all studied compositions promoted significant wear on
the granite and steel discs. Samples with lower Ta quantity demonstrated severest wear,
while the other compositions followed a descending wear trend with increasing binder
percentage.
- Wear phenomena were more noticeable in steel discs due to the lower hardness of this
material, comparing to granite. Cracks on the granite discs surfaces were also observed
due to the high brittleness of this ceramic.

90
- Abrasive and adhesive were the predominant wear mechanisms detected in all examined
compositions, and their intensities were closely dependent on the binder amount on the
samples.
- Finally, the overall microstructural, mechanical, and tribological outcomes

demonstrated that the developed composites presented satisfactory performance, which
indicates that tantalum can be a viable alternative to act as a PCD binder.

91
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FEDERAL UNIVERSITY OF RIO GRANDE DO NORTE

TECHNOLOGY CENTER (CT)

MATERIALS SCIENCE AND ENGINEERING

Development of a novel polycrystalline diamond

Regina Bertília Dantas de Medeiros

Advisor: Prof. Dr. Uílame Umbelino Gomes

Natal – RN, Brazil

REGINA BERTÍLIA DANTAS DE MEDEIROS

Development of a novel polycrystalline diamond

Master's thesis presented to the Materials Science

Advisor: Prof. Dr. Uílame Umbelino Gomes

Natal– RN, Brazil

Regina Medeiros, 2021 PPgCEM/UFRN

Medeiros, Regina Bertília Dantas de.

Dissertação (Mestrado) - Universidade Federal do Rio Grande

1. PCD - Dissertação. 2. Tribology - Dissertação. 3. High

RN/UF/BCZM CDU 620.1

Elaborado por RAIMUNDO MUNIZ DE OLIVEIRA - CRB-15/429

Dedicated to all scientists, researchers and

Regina Medeiros, 2021 PPgCEM/UFRN

I am grateful to Prof. Rubens Maribondo do Nascimento and Prof.ª Alessandra Agna

I would especially like to express my eternal and unconditional gratitude to my family.

All my gratitude to my wonderful Diamond Group, especially to my dear friends Diego

I acknowledge all the team of Advanced Materials Laboratory (LAMAV/UENF),

Regina Medeiros, 2021 PPgCEM/UFRN

I extend my sincere thanks to the technicians of Structural Characterization of Materials

Regina Medeiros, 2021 PPgCEM/UFRN

“A diamond is a chunk of coal that did well under pressure”

Regina Medeiros, 2021 PPgCEM/UFRN

Keywords: PCD, Tantalum, Tribology, High Pressure-High Temperature sintering,

Regina Medeiros, 2021 PPgCEM/UFRN

O diamante policristalino (PCD) é um material amplamente aplicado nas indústrias de

Palavras-chave: PCD, Tântalo, Tribologia, Sinterização via Altas Pressões-Altas

Regina Medeiros, 2021 PPgCEM/UFRN

Medeiros, R. B. D.; Barreto, L.P.P.; Gurgel, D. P.; Mashhadikarimi, M.; Guimarães

Gurgel, D. P.; Medeiros, R. B. D.; Barreto, L.P.P.; Mashhadikarimi, M.; Guimarães

Regina Medeiros, 2021 PPgCEM/UFRN

LIST OF ABREVIATIONS AND NOMENCLATURE

Regina Medeiros, 2021 PPgCEM/UFRN

SiC – Silicon carbide

Regina Medeiros, 2021 PPgCEM/UFRN

Regina Medeiros, 2021 PPgCEM/UFRN

Figure 27: Schematic configuration of pin-on-disc apparatus. ..................................... 56

Regina Medeiros, 2021 PPgCEM/UFRN

Regina Medeiros, 2021 PPgCEM/UFRN

Table 1: Main properties of diamond and graphite. ...................................................... 28

Regina Medeiros, 2021 PPgCEM/UFRN

Regina Medeiros, 2021 PPgCEM/UFRN

4.1.1 Effect of milling on powder homogenization ................................................ 61

Regina Medeiros, 2021 PPgCEM/UFRN

Regina Medeiros, 2021 PPgCEM/UFRN

The manufacturing industry plays an indispensable role within the global

Polycrystalline diamond (PCD) is an advanced material known for its unique

Frequently, PCD is described as a composite of micron-sized diamond grains

Regina Medeiros, 2021 PPgCEM/UFRN

Due to the problems encountered by conventional binders, researchers have

With properties similar to those of niobium, tantalum has been receiving

Regina Medeiros, 2021 PPgCEM/UFRN

1.1 Main Goal

This work aims to study the applicability of tantalum as a novel polycrystalline

1.1.1 Specific Goals

d) Study the tribological behavior of PCD-Ta system on ferrous and ceramic