UDK 621.9.02:628:477.

6 ISSN 1580-2949
Professional article/Strokovni ~lanek MTAEC9, 47(1)115(2013)

E. ALTUNCU et al.: CUTTING-TOOL RECYCLING PROCESS WITH THE ZINC-MELT METHOD

CUTTING-TOOL RECYCLING PROCESS WITH THE

ZINC-MELT METHOD FOR OBTAINING
THERMAL-SPRAY FEEDSTOCK POWDER (WC-Co)
POSTOPEK RECIKLIRANJA ORODIJ ZA REZANJE Z METODO
TALJENJA V Zn ZA PRIDOBIVANJE PRAHU WC-Co ZA
TERMI^NO NABRIZGAVANJE

Ekrem Altuncu1, Fatih Ustel2, Ahmet Turk3, Savas Ozturk4, Garip Erdogan2
1Sakarya University, Tech. Fac., Dept. Metallurgical and Materials Eng. Sakarya, Turkey
2Sakarya University, Eng. Fac., Dept. Metallurgical and Materials Eng. Sakarya, Turkey
3Celalbayar University, Eng Fac., Dept. Metallurgical and Materials Eng. Manisa, Turkey
4Ýzmir K. Çelebi University, Eng Fac., Dept. Metallurgical and Materials Eng. Ýzmir, Turkey
[email protected]

Prejem rokopisa – received: 2012-08-16; sprejem za objavo – accepted for publication: 2012-09-19

Various recycling processes for WC-Co cermets from cutting tools, such as chemical modification, thermal modification, the
cold-stream method and the electrochemical method have been investigated and some of them are actually employed in industry.
However, these conventional methods have many problems to be solved and they are not always established technologies.
Therefore, a more economical and high-efficiency recycling procedure needs to be developed. In this study we investigated the
applicability of the zinc-melt method (ZMM) for recycling WC-Co as a powder from cutting-tool scraps. It was proven that
ZMM is an available technique for recovering the WC powder from the cutting tools. WC-Co powders are recovered and then
spray dried, sintered and obtained as a feedstock material for thermal-spray coating processes.
Keywords: cutting tool, WC-Co, recycling, zinc-melt method, spray dryer

Preiskovane so bile razli~ne metode za recikliranje cermetov WC-Co iz orodij za rezanje, kot so kemijska modifikacija,
termi~na modifikacija, metoda s hladnim tokom in elektrokemijska metoda, nekatere od njih pa se `e uporabljajo v industriji.
Vendar pa imajo te konvencionalne metode veliko problemov, ki jih je treba re{iti in nimajo vedno ustaljene tehnologije. Zato je
treba razviti bolj ekonomi~ne in visoko zmogljive postopke recikliranja. V tej {tudiji je bila preu~evana uporabnost metode s
taljenjem odpadkov rezilnih orodij v cinku (ZMM) za recikliranje WC-Co v obliki prahu. Dokazano je bilo, da je ZMM
uporabna tehnika za pridobivanje WC-prahu iz orodij za odrezavanje. WC-Co-prahovi so bili najprej pridobljeni, nato posu{eni
z razpr{evanjem ter sintrani v obliko, primerno za termi~no nabrizgavanje prevlek.
Klju~ne besede: orodje za rezanje, WC-Co, recikliranje, metoda s taljenjem cinka, su{enje z razpr{evanjem

significant. Globally, one third of the consumption of

1 INTRODUCTION WC for the cutting tools is being produced from their
The $2-billion, worldwide tungsten-carbide industry scrap. In recent years, a new technique for recovering
generates large quantities of scrap due to the parts WC and Co from the hard cutting-tool scraps using a
rejected at various stages of the production and the molten-zinc (Zn) bath has been studied. Due to its
worn-out cutting tools. The most basic recycling efficiency and applicability, the zinc-melt process is
approach would be to break down the scrap pieces into considered to have a higher potential for recycling the
powders and then fabricate more WC-based cutting cutting tools3. In this study, the zinc-melt-method
tools. This approach would cause a severe equipment parameters, such as temperature and time were
wear due to the abrasive nature of the cutting-tool mater- optimized. A biscuit-structured WC-Co bulk was ground
ials and is, therefore, not feasible. As a result, the to obtain fine powders and then mixed with a Co powder
recycling is done by chemical means, such as the zinc- by ball milling. These powders were produced with a
recovery process, electrolytic recovery, and extraction by spray dryer, having a spherical form and utilizing the
oxidation. The conventional recycling processes for thermal-spray process (Figure 1). The microstructure
cutting tools have many problems to be solved, so they and chemical properties of these powders were studied
are not efficient technologies. One of them takes a very with SEM and XRD.
long processing time and the other requires high-scale
equipment. Another process leads to decomposition and 2 EXPERIMENTAL WORK
an undesirable phase occurrence. The recycling rate of
WC-Co is only about under 20 % and the rates are still The powder microstructures and surface morpho-
low1–5. Nowadays, the approaches to recovering WC and logies were examined with the scanning electron
Co materials are not only economically important but microscopy (SEM). An elemental distribution analysis of
also, due to the environmental factors, ecologically the recovered powder was conducted with the energy-

Materiali in tehnologije / Materials and technology 47 (2013) 1, 115–118 115

E. ALTUNCU et al.: CUTTING-TOOL RECYCLING PROCESS WITH THE ZINC-MELT METHOD

Figure 1: Experimental route of recycling scrap cutting tools

Slika 1: Eksperimentalna pot recikliranja odpadkov rezilnih orodij

dispersive X-ray spectroscopy (EDS). The crystalline can be sorted into medium (1.2–2 mm), coarse (»4 mm),
phases were identified with the X-ray diffractometry and mixed grain sizes with optical microscopy and by
(XRD). The density of the sintered body was measured composition with x-ray spectroscopy before the zinc-
in water using the Archimedes method. The flowability recovery process. When the WC-Co scraps are dipped in
was measured with a Hall flowmeter. The particle-size a molten-zinc bath, the molten zinc starts to penetrate the
distribution was measured with a laser particle sizer. WC particles and the dissolving Co binder, i.e., the Co
film between the WC particles. The dissolution of the Co
film results in a separation of the WC particles and
3 ZINC-MELT-METHOD (ZMM) RECYCLING
independent particles float in the molten Zn-Co alloy.
PROCESS
Since zinc has a high vapor pressure, it is easily removed
In a zinc-recovery process, cemented carbide scraps in vacuum condition after the separation of WC particles.
are immersed in molten zinc in an electrical furnace at As zinc evaporates under vacuum, the Co content
1 atmosphere of inert gas at 650–800 °C. The zinc is gradually increases and the Co metal has to precipitate
subsequently distilled at 700–950 °C.6,7 The optimum on the WC surface from the molten alloy. When zinc
conditions depend on the Co content and the zinc-to- evaporates completely, all Co precipitates on the WC
cobalt ratio. The properties of the reclaimed powders are particle surface resulting in the WC-Co powders with the
the same as the virgin powders. Scrap cemented carbides same chemistry as found in the original powder before

Figure 2: Zinc-melt process8

Slika 2: Postopek s taljenjem v cinku8

Figure 3: Recycling process of WC-Co

Slika 3: Postopek recikliranja WC-Co

116 Materiali in tehnologije / Materials and technology 47 (2013) 1, 115–118

 E. ALTUNCU et al.: CUTTING-TOOL RECYCLING PROCESS WITH THE ZINC-MELT METHOD

Table 1: Biscuit structures after different thermal treatments

Tabela 1: Kola~i, dobljeni po razli~nih termi~nih obdelavah

the sintering8 (Figures 2 and 3). By increasing the granules having a large variety of shapes – from the
process temperature and time, the recycling efficiency uniform solid spheres, which are regarded as ideal
was improved. The zinc contamination was reduced granules for most ceramic systems, to elongated, pan-
(Table 1). cake, donut-shaped, needle-like or hollow granules9–11.
Process specifications: Process temperature: 700–900 °C The spray-drying process transforms a solution with a
under Ar+N2 atmosphere, Melting time: 1–10 h, Charge: certain solid content into a powder of the solid in one
14–22 kg (Scrap/Zn:1/ 1.3), Efficiency: 82–97 %. step. In this study we used volume fractions 25 %
WC-Co + water solution (slurry). The solid aggregates
are collected at the bottom of the chamber and separated
4 SPRAY DRY PROCESS
from the gas in cyclone collectors. The main controlled
Spray drying which is the most versatile powder- operating parameters are the air temperature at the entry
processing method consists of spraying a water-based (185–210 °C), at the exit (100–140 °C) and inside the
suspension (called slurry) of the materials to agglome- chamber (165–180 °C), the atomizing nozzle design and
rate into a stream of heated air. The rapid heat and mass the air- and slurry-flow rates. The flowability of thermal
transfer which occurs during the drying combined with spraying is good. The mean particle size is D50 » 48 μm.
the presence of various slurry compounds result in dried According to the X-ray diffraction (XRD) investigations

Figure 4: Spray-dried powders and deposition

Slika 4: Prah, osu{en z razpr{evanjem in po depoziciji

Materiali in tehnologije / Materials and technology 47 (2013) 1, 115–118 117

E. ALTUNCU et al.: CUTTING-TOOL RECYCLING PROCESS WITH THE ZINC-MELT METHOD

of the spray-dried feedstock presented earlier, WC, WC2, crystallinity and flowability properties. These powders
WO3, CoWO4 and metallic Co were present. The feed- can be easily used in the HVOF process. However, prior
stock powder consisted of a-few-micrometers-sized to starting further production of the recycled WC/Co
agglomerates where the WC particles of 1–5 μm were powders, it will have to be demonstrated that this is a
finely distributed in the Co matrix. cost-effective production.
Figure 4 shows the variety of shapes: from uniform
solid spheres to elongated, pancake, donut-shaped,
Acknowlodgements
needle-like or hollow granules. It was found that the
higher the inlet temperature, the faster is the moisture The author is thankful to the members of the Sakarya
evaporation. A higher outlet temperature leads to a larger University Thermal Spray Laboratory.
size of the powder. And the outlet temperature also
controls the final moisture content of the powder. As the
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118 Materiali in tehnologije / Materials and technology 47 (2013) 1, 115–118