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Non-homogeneous structures in cemented carbides
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Properties.ORCID iD: 0000-0002-6987-6153
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Cemented carbides are composite materials traditionally consisting of hard ceramic tungsten carbide (WC) particles, commonly referred to as WC grainsand metallic cobalt (Co) matrix. This is a combination that gives the material aunique set of properties, combining high hardness and toughness that are suitable for demanding applications such as rock drilling or metal cutting. Depending on application the material properties can be tailored by differentcombinations of WC grain size, metallic binder content and additional hard phases.

In many applications it has been found beneficial to have a variation in microstructure between surface and bulk. Today there are a number of production technologies by which a non-homogenous structure, also called functional gradients, can be produced. These gradients can be generated onvarious length scales. 

In this work, functional gradients, comprising macro gradients on the mm scale, have been produced by modifying the green body before sintering. Here, this means that a grain growth inhibitor, titanium carbide (TiC), has been locally added on the surface of a WC-Binder sample, here WC-Binder means WC-Co, WC-Ni or a WC-Fe composite. These samples are primarily pressed green bodies, but TiC has also been added on sintered materials to study the effect ofporosity on gradient formation in a second sintering. By locally adding TiC an alternative way of introducing a grain growth inhibitor is explored. This approach allows for sustainable use of raw materials, by introducing the TiCwhere it is needed. Upon sintering, Ti and C diffuses into the WC-Binder bulk affecting the structure and composition, and a non-homogenous material is created. 

The sintered samples have been manufactured through standard metallurgical procedures and extensively studied using microscopy and microanalysis. Within the scope of this thesis, different parameters, such as; WC raw material, sintering temperature and porosity are investigated in the WC-Co system to learn how they influence the final structure in the sintered composite material. The possibility to extend functional gradient sintering, producing macro gradients, to include alternative binders, Nickel (Ni) and Iron (Fe) is also investigated. 

In these gradient materials, a relation exists between the diffusion of Ti and C from the applied TiC layer and the growth of WC grains in the bulk material. This relation becomes particularly evident under conditions that promote WC grain growth, such as elevated sintering temperatures or the use of small initial WC powder sizes. Also binder chemistry affects the WC grain growth. The developed compositional and structural gradients can be related to the mechanical properties, and a higher hardness is achieved at the surface of the TiC addition compared to the bulk material. A comparable hardness gradient is observed in samples with Ni and Co binders, while those with Fe binders display a less pronounced gradient. 

To complement the experimental work, diffusion modelling has also been applied to better understand and predict the gradient formation for varying sintering temperatures and binder chemistries. The model accurately reflects the trends in Ti gradient formation but careful consideration of the system, for example WC raw material and amount of TiC addition is needed to understand and make use of the model results. 

The results from this thesis can contribute to the understanding and further development of sustainable tool materials for industrial implementation.

Abstract [sv]

Hårdmetall är ett kompositmaterial som traditionellt sett består av hårda keramiska partiklar av volframkarbid och en metallisk bindefas av kobolt. Detta är en kombination som ger materialet unika egenskaper av hårdhet och seghet som lämpar sig till verktyg för till exempel bergborrning eller skärande bearbetning. Olika kombinationer av volframkarbidens storlek och mängd bindefas ger olika materialegenskaper som kan skräddarsys.  

Man har i många tillämpningar funnit det gynnsamt att ha en variation i mikrostrukturen mellan yta och bulk. Idag finns det ett antal tillverkningsprocesser genom vilka en varierande mikrostruktur kan tillverkas så kallade funktionella gradienter. Dessa kan skapas i olika längdskalor. 

I detta arbete har funktionellagradienter, bestående av makrogradienter i mm-skala, producerats genom att modifiera grönkroppen före sintring. Här innebär detta att en korntillväxthämmare titankarbid lokalt har tillsatts på ytan av en grönkropp av hårdmetall. Den lokala tillsatsen har applicerats främst på pressade grönkroppar men titankarbidtillsatsen har också gjorts till sintrade prov för att studera effekten av porositet på gradientbildningen. 

De sintrade proverna har tillverkats genom en standardmetallurgisk process och noggrant studerats med hjälp av karakteriseringstekniker, så som mikroskopi och mikroanalys.  

Inom ramen för denna avhandling undersöks olika parametrar, såsom val av volframkarbidens råmaterial, sintringstemperatur och initial porositet i volframkarbid-kobolt systemet för att utforska hur dessa påverkar den slutliga strukturen i det sintrade materialet. Vidare undersökts möjligheten att utöka funktionellgradientsintring till att inkludera andra bindefaser så som nickel och järn.   

Lokal tillsats av titankarbid utforskar ett alternativt sätt att tillsätta en korntillväxthämmare. Detta möjliggör hållbar användning av råmaterialet genom att tillsätta det där det verkligen behövs. Vid sintringen diffunderar titan och kol in i hårdmetallen och påverkar strukturen och sammansättningen, och ett icke-homogent material skapas. Vid skapandet av dessa funktionella gradienter finns en koppling mellan titandiffusionen från det applicerade titankarbidlagret och tillväxten av volframkarbidkornen i bulkmaterialet. Denna koppling blir särskilt tydlig under förhållanden som främjar korntillväxten för volframkarbidkornen, såsom förhöjda sintringstemperaturer eller användning av små initiala partikelstorlekar för volframkarbiden. Även bindefasens kemi påverkar volframkarbidkornens tillväxt. 

De utvecklade samansättning- och strukturgradienterna återspeglas i de mekaniska egenskaperna. På detta sätt fås en högre hårdhet vid ytan där titankarbidtillsatsen gjorts jämfört med bulkmaterialet. En liknande hårdhetsgradient observeras i prover med nickel- och koboltbindefas, medan det prov med järnbindefas uppvisar en mindre gradient.  

Diffusionsmodellering har också använts för att förstå och förutsäga gradientbildningen vid varierande temperatur och bindefasskemi. Modellen återspeglar trenderna i titangradientbildningen, men kunskap om systemet, till exempel vilken råvara för volframkarbiden som använts och/eller mängden titankarbidtillsats, behövs för att förstå och kunna använda modellresultaten.  

Resultaten och kunskapen från denna avhandling bidrar till ökad förståelse av dessa system och kan på så sätt användas för vidareutvecklingen av hållbara verktygsmaterial för industriell implementering. 

 

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2025. , p. 54
Series
TRITA-ITM-AVL ; 2025:20
Keywords [en]
Cemented carbide, Hard metal, Functional gradient material, macro gradients,  Alternative binder, Grain growth inhibition
National Category
Other Materials Engineering
Research subject
Materials Science and Engineering
Identifiers
URN: urn:nbn:se:kth:diva-363551ISBN: 978-91-8106-327-1 (print)OAI: oai:DiVA.org:kth-363551DiVA, id: diva2:1959112
Public defence
2025-06-16, D3 / https://kth-se.zoom.us/j/69595764136, Lindstedtvägen 9, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2025-05-21 Created: 2025-05-19 Last updated: 2025-06-30Bibliographically approved
List of papers
1. Development of a functional hardness gradient in WC-TiC-Co cemented carbide during gradient sintering
Open this publication in new window or tab >>Development of a functional hardness gradient in WC-TiC-Co cemented carbide during gradient sintering
2023 (English)In: International journal of refractory metals & hard materials, ISSN 0263-4368, Vol. 115, article id 106293Article in journal (Refereed) Published
Abstract [en]

In this study two functionally graded cemented carbide samples with gradients in both composition and grain size have been produced and studied. The two samples are manufactured by local addition of TiC to a pressed WC-Co green body prior to sintering. The two samples differ only by the in-going WC particle size, where one sub-micron and one coarse WC particle size is used. The Ti, Co, and C concentration profiles are analysed using energy−/ and wavelength-dispersive X-ray spectroscopy; Vickers hardness profiles are also measured. Furthermore, the measured experimental concentration profiles are compared with diffusion simulations using the DICTRA software. The concentration and hardness profiles show a similar trend for both samples with decreasing Ti and C concentrations while Co concentration increases with distance from the applied TiC layer. The composition gradient affects the number of stable phases and the WC grain size. Furthermore, there are distinct differences between the samples with different initial WC particle size. The sample with an initially finer WC particle size has a shorter gamma-phase zone and the difference in WC grain size across the gradient is larger as compared to the sample with an initially coarser WC particle size. Finally, abnormal grain growth occurs in both samples but it is suppressed with increasing Ti concentration.

Place, publisher, year, edition, pages
Elsevier BV, 2023
Keywords
Cemented carbide, Functional gradient material, Grain growth, Sintering
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:kth:diva-331431 (URN)10.1016/j.ijrmhm.2023.106293 (DOI)001020441000001 ()2-s2.0-85161690245 (Scopus ID)
Note

QC 20230710

Available from: 2023-07-10 Created: 2023-07-10 Last updated: 2025-05-19Bibliographically approved
2. Gradient Structure Evolution During Sintering of WC-TiC-Co Cemented Carbides
Open this publication in new window or tab >>Gradient Structure Evolution During Sintering of WC-TiC-Co Cemented Carbides
2025 (English)In: JOM: The Member Journal of TMS, ISSN 1047-4838, E-ISSN 1543-1851, Vol. 77, no 4, p. 1979-1991Article in journal (Refereed) Published
Abstract [en]

Functional gradient sintering of WC-TiC-Co cemented carbides was studied to reveal the effect of powder metallurgical processing conditions on compositional and microstructural, as well as hardness and toughness, gradients. The samples were created by local addition of TiC prior to sintering. Two different starting WC powders, one sub-micron and one medium-coarse, were used. Sintering at two different temperatures of 1410°C and 1475°C was compared. The local addition of TiC created a Ti/Co gradient that affected the structural evolution during sintering. The measured Ti/Co gradient after sintering at 1410°C and 1475°C differed, and the difference was especially apparent for the sample prepared using a sub-micron powder. After sintering at 1475°C, the sample prepared from the sub-micron powder exhibited a large WC grain size gradient and elongated or plate-like WC grains where the Ti concentration was high. In contrast, the sample prepared from the medium-coarse powder only showed a WC grain size gradient and no plate-like WC grain formation. It was also observed that the WC grain surfaces had growth ledges in both samples when the Ti content was enhanced, indicating the influence of Ti on the WC grain growth mechanism.

Place, publisher, year, edition, pages
Springer Nature, 2025
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:kth:diva-363585 (URN)10.1007/s11837-025-07127-2 (DOI)001415159100001 ()2-s2.0-85218816250 (Scopus ID)
Funder
Swedish Foundation for Strategic Research, RMA15-0062KTH Royal Institute of Technology
Note

QC 20250519

Available from: 2025-05-19 Created: 2025-05-19 Last updated: 2025-05-19Bibliographically approved
3. Functional-gradient WC-TiC cemented carbides with alternative binders (Ni and Fe)
Open this publication in new window or tab >>Functional-gradient WC-TiC cemented carbides with alternative binders (Ni and Fe)
2025 (English)In: International journal of refractory metals & hard materials, ISSN 0263-4368, Vol. 131, article id 107214Article in journal (Refereed) Published
Abstract [en]

In this work we investigate the development of functionally graded cemented carbides, featuring macro gradients on the millimeter scale, where Fe, or Ni is the binder phase. Two composites, WC-Ni and WC-Fe with 20 % binder by volume were produced by addition of TiC on the surface of the samples before sintering at 1475 °C for 1 h. The sintered samples were analyzed using electron microscopy and microanalysis. For the Ni-binder sample, the results show a clear WC grain size gradient, with the smallest average grain size close to the TiC layer. This sample also exhibits compositional gradients, where Ni increases while Ti and C decrease from the added TiC layer and outward. The same effect of TiC addition on WC grain growth is observed in the Fe-binder sample, however, the effect is much smaller. The addition of Ti is known to influence the morphology of WC grains in Co-binder systems, and this effect is observed here in both Ni- and Fe-binder samples. WC growth ledges areobserved on the WC facets near the applied TiC layer where Ti levels in the binder are high. This suggests that the WC grain growth inhibition mechanism imposed by Ti is similar in these alternative binders as what has previously been reported for conventional Co-binders.

Place, publisher, year, edition, pages
Elsevier BV, 2025
Keywords
Alternative binder, Cemented carbide, Functional gradient material, Grain growth inhibition, Macro gradients
National Category
Other Materials Engineering
Identifiers
urn:nbn:se:kth:diva-363404 (URN)10.1016/j.ijrmhm.2025.107214 (DOI)001490230400001 ()2-s2.0-105004414736 (Scopus ID)
Note

QC 20250516

Available from: 2025-05-15 Created: 2025-05-15 Last updated: 2025-07-03Bibliographically approved
4. Effect of porosity on fuctional gradient formation in WC-TiC-Co cemented carbides
Open this publication in new window or tab >>Effect of porosity on fuctional gradient formation in WC-TiC-Co cemented carbides
(English)Manuscript (preprint) (Other academic)
Abstract [en]

In this study, local additions of TiC were made to sintered WC-Co cemented carbide samplesand compared with those made to pressed powder compacts. This allows for investigating theeffect of porosity on the reaction sintering between the TiC addition and the WC-Co bulk. Aftersintering, a pronounced Ti gradient is observed in the samples that have been sintered prior tothe TiC addition. WC grain growth inhibition effect caused by Ti is evident due to the developedTi gradient. This effect is also observed in samples with low TiC additions, below the solubilitylimit of the (Ti,W)C γ-phase at the sintering temperature.

Keywords
Porosity, reaction sintering, functional gradient sintering, cemented carbides
National Category
Other Materials Engineering
Identifiers
urn:nbn:se:kth:diva-363588 (URN)
Note

QC 20250519

Available from: 2025-05-19 Created: 2025-05-19 Last updated: 2025-05-19Bibliographically approved

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