F LI NTSTO N E 2 0 2 0
Next generation of superhard non-CRM materials and solutions in tooling
Duration: 2016-2020 (48 months)
H2020 project
Project number: 689279
H2020-SC5-2015-one-stage
SC5-12b-2015 Materials under extreme conditions Keywords: Materials engineering (biomaterials, metals, ceramics, polymers, composites, etc.) Environment, resources and sustainability Natural resources and environmental economics
Document date: March 2020
This project has received funding from the European Commission in the Horizon 2020 program. 2016-2020
Abstract
1
2
3
Relevance
Material dependency
Consor tium par tners
5 Complexit y and focus ar eas
9
10
11
Rock cut ting: diamond/coba lt
Rock cut ting mechanisms
Response I: Investigate tough binders
13
14
Demonstration in an industr y-r elevant environment
Economic impact
4 Project structur e
6
7
8
Fundamental knowledge development on metal and rock cut ting
Joint problems in metal and rock cut ting
Metal cut ting mechanisms
12 Response II: Binders that suppor t c ontrolled decomposition
15
16
Ecological assessment
Overall impact
Imprint
Abstra c t
Flintstone2020 has been an EU-funded Horizon2020 project, which ran from February 2015 until January 2020. The project aimed to replace critical raw materials, Tungsten (W) and Cobalt (Co), from tools in metal and rock cutting, two very large application areas using many critical raw materials. The challenge to solve in Flintstone2020 was to ensure that with these novel materials, the tools would be resistant for deterioration during use, which is under extreme conditions. The consortium has looked into novel materials, using tough binders, but also into creating a protective layer, for instance by controlled decomposition. Several novel materials have been chosen for demonstration at industry-relevant scale, with promising outlook, leading to at least 3 patents filed.
consumer products
ICT applications
transpor t & vehicles
mining/metal industry
forestry/ paper industry
pharma/ biotech
aerospace industry
environmental clean technologies
1 Re leva nc e
The use and manufacture of tools has driven human technology and economy ever since prehistroic times. Tools from flintstone, one of the first hard materials used by humanity, were also among the first trans-regionally traded goods, spreading over hundreds or even thousands of kilometers from their original location – in Europe and many other places in the world. In the last century, the sector of hard materials, and hence tooling, has seen great advances, such as the invention of cemented carbide (a composite mainly consisting of tungsten carbide and cobalt, WC-Co), man-madediamond and the fully-synthetic hard material cubic boron nitride (cBN) with no analogue in nature. At present, many industries depend on these materials, ranging from consumer products, to transportation and vehicles, mining and metal industry, to aerospace and cleaning technology, but these materials themselves unfortunately depend on Critical Raw Materials, such as tungsten and cobalt. As currently more than 80 percent of the entire global tooling market in metal cutting alone is crucially dependent on critical and scarce raw materials, the Flintstone2020 project aims to reduce these critical raw materials in the manufacturing of tools.
1
2
H
He
1.008 Hydrogen
3
4
Li
6.94 Lithium
11
Na
22.98976928 Sodium
19
4.002602 Helium
Rb
85.4678 Rubidium
55
Cs
132.90545196 Caesium
87
Fr
223 Francium
13
Mg
24.305 Magnesium
Ca 40.078 Calcium
38
Sr
87.62 Strontium
56
Ba Ra
21
Sc
Actinide Series
22
44.955908 Scandium
39
Y
88.90584 Yttrium
40
Zr
89 103
La
Ac
227 Actinium
Hf
178.49 Hafnium
104
Rf
58
Ce
140.116 Cerium
90
Th
232.0377 Thorium
V
50.9415 Vanadium
41
Nb
92.90637 Niobium
73
Ta
24
105
Db
268 Dubnium
59
Pr
140.90766 Praseodymium
91
Pa
231.03588 Protactinium
Cr
51.9961 Chromium
42
Mo
95.95 Molybdenum
74
180.94788 Tantalum
267 Rutherfordium
138.90547 Lanthanum
89
23
91.224 Zirconium
71
57
Ti
47.867 Titanium
72
57
226 Radium
Lanthanide Series
C
Al
W
25
Mn
Sg
43
Tc
98 Technetium
75
Nd
144.242 Neodymium
92
U
238.02891 Uranium
Re
186.207 Rhenium
107
Bh
269 Seaborgium
60
Fe
54.938044 Manganese
183.84 Tungsten
106
26
55.845 Iron
44
101.07 Ruthenium
76
Os
Pm
145 Promethium
93
Np
237 Neptunium
Co
108
Hs
269 Hassium
62
Sm
150.36 Samarium
94
Pu
244 Plutonium
28
58.933194 Cobalt
45
Rh
102.90550 Rhodium
77
Ir
109
Mt
278 Meitnerium
63
Eu
151.964 Europium
95
Am
243 Americium
Ni
29
58.6934 Nickel
46
Pd
78
Pt
195.084 Platinum
110
Ds
281 Darmstadtium
64
Gd
157.25 Gadolinium
96
Cm 247 Curium
Cu
30
Zn
63.546 Copper
47
Ag
106.42 Palladium
192.217 Iridium
190.23 Osmium
270 Bohrium
61
Ru
27
107.8682 Silver
79
Au
196.966569 Gold
111
Rg
281 Roentgenium
65
Tb
158.92535 Terbium
97
Bk
247 Berkelium
31
Ga
65.38 Zinc
48
Cd
69.723 Gallium
49
112.414 Cadmium
80
Hg
14
Si
Cn
285 Copernicium
66
Dy
162.500 Dysprosium
98
Cf
251 Californium
28.085 Silicon
32
Ge
72.630 Germanium
50
Sn
114.818 Indium
81
Tl
200.592 Mercury
112
In
118.710 Tin
82
Pb
204.38 Thallium
113
Uut
286 Ununtrium
67
Ho
164.93033 Holmium
99
Es
252 Einsteinium
7
N
12.011 Carbon
26.9815385 Aluminium
137.327 Barium
88
6
10.81 Boron
12
39.0983 Potassium
37
B
9.0121831 Beryllium
20
K
5
Be
207.2 Lead
114
Fl
289 Flerovium
68
Er
167.259 Erbium
100
Fm
257 Fermium
8
O
14.007 Nitrogen
15
P
15.999 Oxygen
16
S
30.973761998 Phosphorus
33
As Sb
121.760 Antimony
83
Bi
208.98040 Bismuth
115
Uup
289 Ununpentium
69
Tm
168.93422 Thulium
101
Md
258 Mendelevium
F
34
Se
17
Cl
Te
127.60 Tellurium
84
Po
35
Lv
293 Livermorium
70
Yb
173.054 Ytterbium
102
No
259 Nobelium
20.1797 Neon
18
Ar
Br
39.948 Argon
36
Kr
79.904 Bromine
53
I
126.90447 Iodine
85
209 Polonium
116
Ne
35.45 Chlorine
78.971 Selenium
52
10
18.998403163 Fluorine
32.06 Sulfur
74.921595 Arsenic
51
9
At
210 Astatine
117
83.798 Krypton
54
Xe
131.293 Xenon
86
Rn 222 Radon
118
Uus Uuo
294 Ununseptium
71
Lu
174.9668 Lutetium
103
Lr
266 Lawrencium
294 Ununoctium
2 Ma teria l de pende nc y
The overall aim of this project is to provide a perspective for the replacement of two important CRMs – tungsten (W) and cobalt (Co) – which are the main constituents for two important classes of hard materials (cemented carbides(WC-Co), and PCD(diamond-Co) – by developing innovative alternative solutions for tooling and operating under extreme conditions The EU is heavily dependent on imports of tungsten and cobalt. The EU’s assets of tungsten makes up only about 2% of the global assets. Yet, the EU consumes 13% of the global supply, an equivalent 12.000 tons (year: 2011). The EU imports the majority of tungsten from China and Russia. In some cases, the fluctuations in pricing were more than 100 %, which indicates the sensitive situation and dependency on raw materials that are crucial for the European industry. The corresponding dependencies of cobalt are not quite as large, but with increasing use within European industry, the availability of this CRM might become equally critical.
Machining applications
Total absolute percentage
Replacement Low risk 95 %
Replacement Medium risk 45 %
Replacement High risk 5%
Comments
Steels
46%
0%
0%
8–10%
Steels with perlitic structure
Stainless steel
18%
4–5%
8–10%
12–14%
Except ferritic structure
Cast Iron
16%
6–8%
8–10%
10–12%
Except ferritic structure
Non-ferrous
7%
2–3%
3–4%
4–5%
Aluminum thin wall castings
Super alloys
10%
2–3%
3–4%
4–6%
Inclusive Ti-alloys
Hardened materials
3%
0.5–1%
1–1.5%
1.5–2%
Die tool production
All applications
100%
14.5–20%
23–29.5%
39.5–49%
Mean yearly replacement of tungsten [tons]
2500
410
660
1005
Estimation based on Monte Carlo simulations
Flintstone 2020 focuses on finding technical solutions, which allows the replacement of CRM-based tools in parts of the selected applications that have a particularly high potential. Moreover, the project targets societal and environmental challenges from EIP on Raw Materials such as: • Reduction of waste generation by a mimnimum of 10% : Flintstone2020 will work on various solutions and strategies to reduce the waste generation of superhard materials, by optimising the yields and developing recycling systems. The utilisation of energy, water, consumables, raw materials, byproducts will be assessed and strategies for mitigation, recovery and use on other industries will be investigated for their eco-efficiency potential. From this aspect, the potential for a cradle-to-cradle utilisation will be analysed though the focus of the project will be cradle-to-grave. • Boosting resource efficiency and promoting recycling, with the activities planned in WP6. • Substituting CRM’s for at least 5 application areas as mentioned in section 2. • Expanding European raw materials knowledge base with information, flows and dynamic modelling system for primary and secondary raw materials.
Sweden
The Netherlands United Kingdom
Germany
Ukraine
France
N
3 Consor tium pa r tne rs
To realise these ambitious plans and activities, the consortium brings together experts from Europe, to collaborate, with their different skills that are linked to the tasks and activities they carry out in the project. Lund University (LU) from Sweden coordinated this project, and has been mainly be responsible for the development of fundamental knowledge on tool wear, performance, and application of non-CRM tool materials and tools. Together with the German TU Bergakademie Freiberg (TUBAF), French CNRS and Ukrainian Institute for Superhard Materials (ISM) experiments have been carried out to bring the innovations to be validated in the lab. The UK-based company, Element 6, together with the research institutes validated novel materials within their industrial pilot equipment for testing under industrial viable conditions. The Swedish companies SECO Tools and Sandvik Mining and Construction Tools (SMC) took the lead in transferring the results to the application areas rock cutting and metal cutting. Moreover, LU collected information to validate the economic viability of the materials and applications, which provides crucial information to the industry parnters for future replication and exploitation, information, which was taken up by the Dutch SME Boukje.com Consulting (BCC). bifa validated the project results on ecologic performance, and assessed the health and safety aspects of the (intermediate) project results to provide this feedback to the partners in an early development stage.
focus area I rock cutting
existing situation materials deteriorate through utilization
focus area II metal cutting
4 P roj ect struc tur e
In order to provide a focus to the research in the Flintstone project, two main application areas have been chosen: on one hand we investigated the challenges related to tools for rock drilling, which is an important focus area for our project partner Sandvik Mining and Construction Tools. On the other hand, we investigated metal cutting, which is an important focus area for our project partner SECO Tools.
response I invest in tough binders
new Polycrystalline cubic Boron Nitride (PcBN)
increased resistance to graphitization for diamond tools
response II create protective layer through controlled decomposition
The project departed from the common problem for those two application areas: the tools need to be resistant for deterioration during use, where they are applied under extreme conditions. The consortium has looked into novel materials, using tough binders, but also into creating a protective layer, for instance by controlled decomposition. Research into the tough binders has lead to new PcBN materials and binders that have increased resistance to graphitization in the case of PCB materials.
Structure
Properties
binder types
hardness
particle size
toughness
particle distribution
elasticity
thermal resistance
Shape
shape options
5 Complex it y a nd focu s ar eas
To design new materials for both selected application areas amounts to addressing the complex interplay of structure, properties and shapes of the tool. When replacing critical raw materials, the structure of the material will change, e.g. its binders (replacing CRM’s or modified binder composition for the novel material), particle sizes or the distribution of the different particles. This in turn, affects the properties of the materials: e.g. toughness, hardness, elasticity and thermal resistance. The accumulated effect of these modifications depends on the shape and the use of the final materials, whether it will be a drill, a sharp cutting tool, or an abrasive tool. Changing the shape of the material has a reciprocal effect on material properties and structure.
feed
temperature
abrasion
pressure
adhesion
relative speed
diffusion
environment
chemical wear mechanism
tribology
oxidation
cutting speed
cutting depth
tool geometry
tool microgeometry
coolant/ lubricant
6 F u nda me nta l knowledge devel o pment o n meta l a nd roc k c u t ting
To provide the crucial fundamental knowledge on wear mechanisms that will accurately deal with the complex, simultaneous interplay of different factors, Flintstone2020 started out with identifying wear mechanisms of reference tool materials in relation to machining operations. Supported by advanced modeling that takes the complex interplay of structure, properties and shapes of the tool all into account, a novel infrastructure for quantitative characterization of individual wear mechanisms was built in order to assess novel materials against reputable references for different tooling applications.
Standard tool at T 1 Standard tool at T0
Improved tool at T 1 Current state-of-the-art tool in terms of structure, properties and shape
7 J oint proble ms in metal and ro ck cut t i ng
In rock cutting as well as in metal cutting, tools are being used under extreme conditions, as they encounter other hard materials, experience extreme heat and sometimes pressure. This causes tool material degradation, both in the binder and the abrasive phase (for diamond and cBN). Standard tools have a “useful tool life�, determined by the complexity of factors as outlined in the previous chapter. Such factors are shape, structure, conditions of use, etc. In order to reduce costs, users of tools are interested in tools that will have a longer tool life, less breakage and less wear. These requirements have to be combined with replacing critical raw materials in the tools, in order to create a sustainable and economic perspective.
tool material microstructure
material deformation zone
material being cut
cutting tool
tool deformation zone
8 Meta l c u t ting mec ha n i sms
The process window for operations for metal cutting, is defined through the complex interplay of workpiece material and shape, versus the cutting tool material (microstructure) and shape. In metal cutting, the tool deforms the material being cut, thus impacting the quality of the produced component. But the tool itself, when interacting with hot metal, is subject to wear and deterioration as well. With many different tool shapes to accommodate many different products (i.e. workpiece materials and shapes and processing conditions), finding the optimum process window for each different workpiece is a challenge, in addition to replacing tooling materials.
Graphitization
Hardness
Development corridor
Relation toughness – hardness Graphite structure
Temperature
Toughness
9 Rock c u t ting : dia mond /co bal t
In order to create novel materials, it is extremely important to know or find the right processing window for the tools that will provide the best result related to end product and tool life. In the case of diamond rock tooling, the potential development corridor is determined by the relationship between toughness and hardness. Rock cutting tools are exposed to severe impact, so tool brittleness cannot be overlooked. Moreover, strategies for dealing with graphitization have to be developed, especially in the case of diamond, which is metastable. Binders that do not suppress graphitization under extreme process conditions make the tool inefficient.
Cemented carbide
Diamond/cobalt
Poor hardness but excellent toughness
Excellent hardness, but is brittle and easily graphitizes
Cemented carbide
Diamond/cobalt
Graphitization
Due to easier abrasion, particles deteriorate and binders disappear
Bridges between particles break
Temperatures over 850C compromise the atomic structure
Polycrystalline diamond materials
10
Combines optimum toughness, hardness and thermal resistance
Ro c k c u t ting mec ha nisms
Due to long exposure to elevated temperatures, as is common in rock cutting, the microstructure of the tool will brittle on its own, becoming more susceptible to breaking, facturing and thus failure. When using conventional cemented carbides, particles are very easily abraded, and binders are abraded or dissolved. When using conventional diamond or cobalt materials, the excellent hardness of these materials are overshadowed by the brittleness of the diamond-diamond bridges between the particles that break easily, as well as by easy graphitization as the temperature influences the atomic structure. The most important challenge is optimizing the relation between toughness, hardness and thermal resistance, in order to provide an optimal solution for tool life and cost effectiveness.
Polycrystalline diamond materials Combines optimum toughness, hardness and thermal resistance
I prevent graphitization
II improve toughness/hardness
III prevent particle deterioration
+ rotational impact
hardness
linear downward impact
toughness
thermal resistance
densely connected tool material
prevents graphitization
tough binders persist even after reinforcement (cBN) particles have been destroyed
material particles/ binders
deteriorating force due to usage
11 Respons e I : investig a t e to ugh bi nders
Within Flintstone2020, many experiments on sintering of diamond- and cBN-based composites at high pressure and high temperature were carried out. These composites have been built with different tough binders that persist even after reinforcement particles (diamond or cBN) have been destroyed by the thermal, physical or chemical loads during operation. More than 300 samples with different binders were sintered and studied, and some of the materials have been through a demonstration procedure at an industry-relevant scale.
decomposition zone/ protective layer
material particles/ binders
deteriorating force due to usage
12 Respons e I I : binders that suppo r t co nt ro l l ed decomposition
The project has investigated binders that support the principle of controlled decomposition: As the binder is attacked by physical and chemical loads, its deterioration productios will remain on the tool surface and keep protecting it. As such the integrity of the tool will deteriorate slower than currently, as the layer may be continuously replaced during use. Within Flintstone2020, several binder systems have been created, evaluated and selected for further testing to provide input into further process and property optimisation.
Economic assessment
Problem/solution pathways
Testing
Demonstration/ upscaling
Ecological assessment
13 De monstra tion in a n i ndust r y-r el evant e nvironme nt
In order to process the novel materials, a new design for a reaction vessel was realised in the project, and several materials were already tested. This reaction vessel has allowed for a wide range of sintering conditions to be accessed by possible material systems. It provided the opportunity to test materials and processes for their respective application areas: metal cutting and mining. In order to reach relevant conclusions on economic viability and sustainablity, standard geometries have been produced with the novel materials. Their performance was tested in terms of use, such as durability, tool life, breakage, and further assessed versus production costs and their environmental impact.
100%
1
share of CRM in total price
2
due to exploding price, this share increases exponentially
3
reduce amount (and share!) of CRMs
4
creating economic margin to prepare for financial competition in future
current price
100%
future price explodes due to CRMs
surpress future price
14 Ec onomic impa c t
We need to develop tools without or with a very limited amount of CRM’s that do not compromise the performance of these tools to be successful, while at the same time providing an attractive price level. To verify the cost effectiveness of our project results, a model that can compare conventional tool materials with the materials has been developed in the Flintstone project. This novel model is taking tool material performance and different application areas into account, based on the input from the project partners. The basic Cost-Performance Ratio (CPR) definition describes the ratio between the maximum allowable prices for the new technology in order to be able to compete with the established or conventional technology
jor
ma ang
of
df fee r ius m ad er ap cut le k
nos
ting
pth
cut
de
equivalent chip thickness (woxĂŠn) cutting speed vx
Process Data
tool material and design
5 Constants work material machinability
K H M N0 L
Estimated Tool Life
Colding’s Equation
tolerance requirements
surface requirements
Wear Criterion
process stability
savings compared to reference (100%)
particulate matter
ionising radiation
water use
photochemical ozone formation
resource use [fossil fuels]
eutrophication [terrestrial]
land use
eutrophication [freshwater]
resource use [minerals/metals]
eutrophication [salt water]
ozone depletion
climate change
acidification
100%
CC Ref (CP500)
25%
CBN Ref (FS120)
25%
cBN New (FS320)
12.5%
cBN New (FS330)
15 Ec olog ic a l a s s es s men t
In order to assess the novel materials with respect to their environmental impact and potential toxicity of materials considered for use, bifa has set up a model to monitor the entire expected life-cycle of the upcoming products, including eco-efficiency of the overall process and reduction/mitigation of waste in its various steps. Combining life-cycle inventory with lifecycle impact analysis and the cost balance sheet, the materials can be assessed for further use in industrial processes and applications.
life cycle inventory analysis goal, scope & definitions
life cycle impact assessment combined environmental impact
ecological assessment cost considerations
data collection
integrated eco-efficiency analysis
costs balance sheet
black-box
powder production
green body production
sintering
grinding
edge preparation
tool use
coating
(final part production)
recycling
90% achieved
envisioned
+600%
achieved
+400%
savings of Cobalt (Co) and Tungsten (W) compared to a reference process envisioned: 50% savings achieved: 90% savings
tool life multiplication compared to reference tools envisioned: +400% achieved: +600%
envisioned
+150%
achieved
CPR indicates that a potential profit of +150% can be achieved compared to standard PCBN
16 O vera ll impa c t
Pushing the EU to the forefront in the area of sustainable raw materials substitution.
Already within the timeframe of the project, 40 publications were published based on the Flintstone2020 results. A major contribution for the development of innovative and sustainable solutions for the substitution of the two critical raw materials (CRMs) tungsten (W) and cobalt in the application field of hard materials for use under extreme conditions was achieved, both in disseminating scientific knowledge, as well as filing novel patents that will provide the participating companies and research institute a cutting edge for exploitation.
Significant contribution to environmental impacts
Based on the research results within the project, the new materials were able to save up to 90% Co and WC compared to reference, exceeding the Flintstone2020 goals of reducing with 50 %. Hence providing a huge positive environmental impact, especially with the promising exploitation opportunities of the materials, to be introduced on the market.
Improved competitiveness
Even without extensive process optimisation, the cost-performance ratio (CPR) of the novel PCD system indicates that a potential profit of up to 150% can be achieved compared to standard PCBN. With a 6-fold improved tooling life for HPHT carbide tool in PCB/PCBM production, results look extremely promising for industries to produce competitive materials and tools, even though the generic results achieved need to be targeted for specific application areas.
IMPRINT
Lunds Universitet
SECO
Volodymyr Bushlya Daniel Johansson Filip Lenrick Jan-Eric Ståhl (coordinator) Christina Windmark
Per Alm Vitaliy Kazymyrovych Stefan G. Larsson-Fritz Rachid M’Saoubi Eva Söderberg Anders Wickman
Technische Universität/Bergakademie Freiberg
Sandvik
Kevin Keller Tania Kolabyli Edwin Kroke Marcus Schwarz
Björn Claesson Edgar Halling Malin Mårtensson Daniel X. Rosén
CNRS
bifa
Vladimir L. Solozhenko Kirill A. Cherednichenko Vladimir A. Mukhanov
Iris Fechner Boris Mertvoy Matthias Seitz Karsten Wambach
ISM
Boukje.com
Oleksandr Osipov Igor Petrusha Kateryna Slipchenko Denys Stratiichuk Volodymyr Turkevych
Karen van den Bos Boukje Ehlen Bas Förster Otto Paans
Element Six
Antionette Can Thomas Griffin Igor Konyashin Ellie Little Miriam Miranda Serdar Ozbayraktar Ross Turner Xiaoxue Zhang
IMPRINT
This project has received funding from the European Commission in the Horizon 2020 program. 2016-2020
PROJECT PARTNERS
Graphic design: Boukje.com Consulting BV