Hard Metal (WC-Co)

Market Processes Quantities Manufacturers Application

Dr. Wolf-W. Albrecht, retired Director of H.C. Starck, Germany Dr. Fritsch Sondermaschinen GmbH, November 2008 For internal use only
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Introduction:

The purpose of this report is to give a short description of markets, processes, quantities, producers and application of hard metal (using WC / Co) worldwide. It shall render the application of the Dr. Fritsch pressure sintering technology clearer and contribute to a more comprehensible discussion on quality parameters of hard metals.

Technical and economic basis:

Tungsten is part of the family of refractory metals, i.e. of elements which are very difficult to produce, due to their high melting temperature (tungsten 3410 among other things. C), Its production therefore - unlike with most other metals - does not take place by means of melting metallurgy but by chemical and/or thermal treatment (see enclosure). The central element of most hard metals is tungsten carbide (WC). It is distinguished for its extreme melting temperature, and especially for an excellent hardness.

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WC powder usually is mixed with Co metal powder (Atritor pulverizing) and, by means of a sintering process (liquid-phase sintering), converted into a solid object, which is denominated hard metal. Its hardness is similar to diamond hardness. This is why its inventors, the Krupp company, also called it Widia (like diamond).

Hard-metal producers worldwide do not only differ with respect to their production method (mixing, pressing, sintering and coating) and to the fields of application (processing of metals, composites, wood etc.) of their products, but also with respect to the WC powder used: - The standard in most companies is the purchase of WC, for example from HC Starck, Wolfram Bergbau, or also from China. Along with cobalt metal powder which is purchased as well, the WC is then processed into hard metal, by mixing, pressing and sintering it. - Some of the very big hard-metal producers such as Mitsubishi MMC, Sumitomo, Iscar / Taegu Tec and recently also Global Tungsten & Powder Group (Metallwerk Plansee / OsramSylvania) dispose of a tungsten chemistry of their own. For Chinese producers, this seems to apply in general. These producers are in a position to process ore (wolframite / scheelite) on plants of their own and to produce WC for their hard-metal production.
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Thanks to its high scrap value, recycling of tungsten scrap has an excellent rank and is therefore applied by many companies, viewing the target of producing WC. These kinds of WC with a frequently higher degree of impurities are added to the clean WC powders.

Further, very big hard-metal producers, such as Sandvik, Seco Tools and Kennametal do not dispose of chemistry plants of their own, but purchase large batches of tungsten compounds such as: ammonium paratungstate (APT) and tungsten oxide (which differs depending on its oxygen contents: blue or yellow oxide; this is important, since different WC qualities result). These compounds are then converted into WC on their own plants. This WC is re-processed into hard metal. Of course, these companies also purchase clean WC.

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Due to its parameters cleanness, grain size and grain distribution, WC has a decisive influence on the quality of the hard metal produced from it. The process of producing WC itself therefore in many cases may not be neglected when assessing the quality of the hard metal.

For a better comprehension of the use of different tungsten products and their processing into hard metal, which is somewhat confusing for outsiders, production methods are represented in the following for:

- Ore processing into ammonium-paratungstate (APT) - From APT to tungsten carbide (WC).

According to todays knowledge, the processes starting from ore and/or alternatively from W-scrap, must be realized in order to produce WC.

Tungsten Market:
According to latest figures (ITIA Meeting Xiamen, Sept. 2008) approx. 88 000 t of tungsten are consumed worldwide.

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Processing of ore into ammonium paratungstate APT

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From APT to WC

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This consumption is subdivided into Western Europe: USA Japan China Russia India 23 000 t 14 000 t 9 000 t 30 000 t 5 000 t 5 000 t

China is hence not only the biggest producer of tungsten worldwide, but also the biggest consumer. Referred to intermediate products which contain tungsten, the following consumption results worldwide (figures referred to Wcontent): WC FeW W - metal products W - compounds W - various 63 000 t 8 000 t 7 000 t 5 000 t 4 500 t

These figures are explained in the following: Hard metal made from WC finds its application in the following sectors, for example: General engineering, automotive engineering, energy and mining.
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FeW serves as alloy component for tool steel and for superalloys. For W-metal products, tungsten powder is used for re-processing in lighting industry, in the manufacture of contacts (with Cu, Ag), in the military sector, for medical engineering and for aircraft construction. Tungsten compounds are used for tungsten chemicals (e.g. W-acid), for catalysts and for hydro-cracking. Various tungsten products are used for surface coating for wear protection and for surface hardening.

From the above figures, it is obvious that more than 70 % of tungsten consumption worldwide refer to WC contained in hard metal.

WC consumption is subdivided as follows (W contents). Western Europe USA Japan China Korea 17 000 t 10 000 t 5 000 t 16 000 t 3 000 t

Russia India

4 000 t 4 000 t

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Western Europe and China are the biggest WC-producing regions worldwide, with an increasing tendency, while production in the USA is stagnating and the quantities produced in Japan are decreasing.

Hard-Metal Manufacture
The process is demonstrated in the following flowchart (manufacturing process of hard metal): Starting from powders such as WC and Co, and, if required, from further carbides, hard metal is manufactured via wet pulverization (Atritor), addition of binder and granulation for improving the flow characteristics during pressing, as well as by pressing, removal of binder, sintering and, sometimes, by repeated surface coating. The sintering step would be the possible application for the Dr. Fritsch pressure sintering technology. Possible tasks from the new sintering technology might result in the following sectors: - process optimization (shorter sintering cycles) - improvement of hard-metal quality (Co loss at high temperatures and long sintering times might be an issue) - reduction of the binder share (Co, Ni) up to processing without binder - use of alternative binders for hard metals.
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Production of Hard Metal

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Depending of the application of the hard metal - just to name some examples: machining of: metals, composites stone / mining / ceramics, oil-well drilling, wood, for drills and cutters, for surface treatment, for hotrolling wear parts as well as projectiles for the military sector, different grain sizes of WC and Co are used. Today, WC kinds from approx. 0.2 m up to 150 m are used, in order to optimize hardness, strength and tenacity.

TaC or other carbides (TiC, TwiC, WTiTaC) are added only in few cases, if, at high temperatures, a corrosion of the hard metal itself has to be feared (example metal machining).

The following chart (ITIA publication) shows some examples of hardmetal composition (WC / Co / Ti, Ta, NbC) with Co shares from 4 to 25 % as well as of the parameters measured at the sintered samples: hardness, transverse rupture strength, fracture toughness, etc. These parameters are decisive for the later use of the hard metal.

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This means that, when using the Dr. Fritsch pressure sintering technology, on the one hand, a variety of production parameters from the way from powder, its processing, up to its application will have to be evaluated when assessing the quality of the sintered samples,

On the other hand, a series of parameters will have to be measured at the sample itself. These parameters will then decide on whether the new sintering technology offers advantages in the manufacturing process of hard metal or with respect to the hard-metal properties. It is recommendable to establish a corresponding test laboratory (hard-metal laboratory) either in the Dr. Fritsch company or to contact a corresponding commercial laboratory.

Manufacturers / Fields of Application

The following chart lists hard-metal manufacturers worldwide, as well as their WC consumption (as W contents) and the fields of application of the hard metals manufactured by them. The chart does not claim to be complete; the quantities are to be considered as approximate. The deduction from worldwide consumption and/or consumption according to continents and/or product sector, however, gives a certain safety that the figures are not completely wrong.
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Manufacturer Henan ZhuZhou CC, Golden Egret, CB Carbide Kennametal Sandvik

Country China USA Sweden Austria / Luxemburg Germany

Application Metal processing / composites All applications All applications Wood / stone processing Metal / composite processing

4 5 6

Ceratizit Ghring, Gelit, Dr. Friedrich TaeguTec / Iscar Seco Tools

ROK / Israel Metal processing / composite Sweden USA Japan Germany USA Germany Japan Japan Japan Israel USA USA Japan All applications Metal processing Metal processing / composite Stone processing / street working Metal / stone processing mining Metal processing / composite Metal processing / composite Metal processing / composite Metal processing / composite Metal processing Metal processing Metal processing / composite

Newcomer, Vista Kyocera, Hitachi, San Alloy

10

Betek Board Longyear Saar Hartmetall Mitsubishi (MMC) Sumitomo Tungaloy (AMC) Iscar

17

Hydrocarbide General Electric Dijet

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Conclusion
Market, process, quantities, manufacturers and fields of application of hard metal (WC/Co) have been summed up briefly, with the aim of providing a basis for a discussion of the use of the Dr. Fritsch highpressure sintering technology. It is obvious that most of the listed parameters have been treated only very briefly and consequently require further explications. This should, however, be the task of a future discussion.

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