FLINTSTONE2020: Next generation of superhard non-CRM materials and solutions in tooling

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