ACTAUNIVERSITATIS

UPSALIENSISUPPSALA

2020

Digital Comprehensive Summaries of Uppsala Dissertationsfrom the Faculty of Science and Technology 1912

Functional properties of siliconnitride based materials for jointapplications

LUIMAR N. CORRÊA FILHO

ISSN 1651-6214ISBN 978-91-513-0891-3urn:nbn:se:uu:diva-406223

Dissertation presented at Uppsala University to be publicly examined in Å4001,Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, Thursday, 23 April 2020 at 09:15 forthe degree of Doctor of Philosophy. The examination will be conducted in English. Facultyexaminer: Professor Julia Shelton (Queen Mary University of London, School of Engineeringand Materials Science).

AbstractCorrêa Filho, L. N. 2020. Functional properties of silicon nitride based materials forjoint applications. Digital Comprehensive Summaries of Uppsala Dissertations from theFaculty of Science and Technology 1912. 60 pp. Uppsala: Acta Universitatis Upsaliensis.ISBN 978-91-513-0891-3.

Total hip and total knee replacements are generally successful procedures for patients sufferingwith pain due to bone fracture or diseases affecting the joints. However, the materials that arecommonly used still have limitations. In particular, corrosion products and wear debris maygive rise to negative body reactions.

In this thesis, silicon nitride based materials were investigated for use in joint implants,namely as a coating for e.g. femoral heads and the metallic modular taper junction in hipimplants, as well as a bulk bioceramic for joint applications. One of the main advantages of thesematerials is the potential to dissolve slowly in aqueous solutions, releasing only biocompatibleions.

To understand the mechanical and wear properties of these materials, thin film coatings weredeposited using magnetron-based techniques onto Si wafers and a CoCrMo alloy, the latterfrequently used in biomedical implants. Coatings up to 8.8 µm thick were deposited on 2Dflat discs as well as full 3D implant heads, following a CrN interlayer for improved adhesion.The chemical composition, microstructure, surface roughness, adhesion, wear resistance, anddissolution properties of the coatings were evaluated as a function of substrate rotation, biasvoltage, target power as well as the addition of different elements.

Results show that it is possible to produce coatings with mechanical properties and a wearperformance similar to bulk ceramics and other ceramic coatings already evaluated in vivo.It was evident that a high coating density is needed, to avoid premature failure in an in vivoenvironment. The coating density, and stability over time in solution, was found to increasewhen a higher target power and process heating were used.

New bulk silicon nitride materials containing only biocompatible additives, were evaluatedfor potential use in joint applications by wear tests for the first time, showing very low wearrates of the counter material.

Silicon nitride coatings and bulk materials tested in this work showed promising results forfurther investigation and a basis for future application in joint bearings.

Keywords: Silicon nitride, Coatings, Wear, Joint replacements, HiPIMS

Luimar N. Corrêa Filho, Department of Engineering Sciences, Applied Materials Sciences,Box 534, Uppsala University, SE-75121 Uppsala, Sweden.

© Luimar N. Corrêa Filho 2020

ISSN 1651-6214ISBN 978-91-513-0891-3urn:nbn:se:uu:diva-406223 (http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-406223)

To my beloved mother Nélcia and maternal grandparents Antônio and

Rita (in memoriam)

Cansaço, fraqueza e dor são passageiros, mas a glória da vitóriaesta é para sempre.

- Ângelo e Cristiano Carioca É necessário sempre acreditar que um sonho é possível que o céué o limite e você é imbatível.

- Racionais MC’s

Cover front page image: Cristina Monte. "Manaus Tecnológica". Na Cuia da Cris, October 24 2019, https://cristinamonte.com.br/manaus-tecnologica/

List of Papers

This thesis is based on the following papers, which are referred to in the text by their Roman numerals.

I Filho, L., Schmidt, S., Leifer, K., Engqvist, H. , Högberg, H. ,

Persson, C. (2019) Towards Functional Silicon Nitride Coatings for Joint Replacements. Coatings, 9(2), 73.

II Filho, L., Schmidt, S., López, A., Cogrel, M., Leifer, K., Engqvist, H. , Högberg, H. , Persson, C. (2019) The effect of coating density on functional properties of SiNx coated im-plants. Materials, 12(20), 3370.

III Filho, L., Schmidt, S., Skjöldebrand, C., Goyenola, López, A.,

Cogrel, M., Leifer, K., Engqvist, H., Högberg, H. Tobler, M., Persson, C. The effect of C, Cr and Nb content on the wear re-sistance of silicon nitride coatings in a hard-on-soft contact. (Submitted)

IV Pettersson, M., Skjöldebrand, C., Filho, L., Engqvist, H., &

Persson, C. (2016). Morphology and dissolution rate of wear debris from silicon nitride coatings. ACS Biomaterials Science & Engineering, 2(6), 998-1004.

V Filho, L., Fu, L., Engqvist, H., Xia, W., Persson, C. Wear per-

formance of a new biocompatible silicon nitride for joint im-plant applications. (Manuscript)

Reprints were made with permission from the respective publishers.

Author’s contributions to the papers

Paper I Part of planning, large part of experimental work (all characteriza- tion except composition analysis) and writing Paper II Part of planning, large part of experimental work (all characteriza- tion except composition and scratch testing) and writing Paper III Part of planning, part of experimental work and major part of

writing Paper IV Part of planning, part of experimental work (SEM characterization

and analysis) and part of writing Paper V Planning, major part of experimental work (all characterization)

and writing

Also published

Kootala, S., Filho, L., Srivastava, V., Linderberg, V., Moussa, A., David, L., & Crouzier, T. (2018). Reinforcing Mucus Barrier Properties with Low Mo-lar Mass Chitosans. Biomacromolecules, 19(3), 872-882.

Bang, L. T., Filho, L. C., Engqvist, H., Xia, W., & Persson, C. (2019). Syn-thesis and assessment of metallic ion migration through a novel calcium carbonate coating for biomedical implants. Journal of Biomedical Materials Research Part B: Applied Biomaterials. 2019; 1- 10. Wei, Z., Romanovski, V., Filho, L., Persson, C., Hedberg, Y.S.,. Metal re-lease from a biomedical CoCrMo alloy in mixed protein solutions under static and sliding conditions – effects of protein aggregation and metal pre-cipitation. Submitted.

Other scientific contributions

Wear resistance of silicon nitride coatings in a hard-on-hard contact Presented at the 3rd International Conference on BioTribology, 11-14 September, London, England, 2016

Wear resistance of silicon nitride coatings in a hard-on-soft contact Presented at the 15th International Symposium on Computer Methods in Biomechanics and Biomedical Engineering, 26-29 March, Lisbon, Portugal, 2018

Wear resistance and ion release of SiNx coatings on CoCrMo full head implants Presented at 18th Nordic Symposium on Tribology, 18-21 June, Uppsala, Sweden, 2018

Effect of Deposition Parameters on the Tribocorrosive Performance of Silicon Nitride Based Coatings Presented at Scandinavian Society for Biomaterials, 12-14 June, Kirkko-nummi, Finland, 2019

Tribocorrosive performance of silicon nitride based coatings in a hard-on-soft contact Presented at European Congress and Exhibition on Advanced Materials and Processes, 1-5 September, Stockholm, Sweden, 2019

Contents

Introduction ................................................................................................... 13

Background - Joint replacements and materials used ................................... 14 Metal alloys .............................................................................................. 15 Polyethylene ............................................................................................. 16 Ceramics ................................................................................................... 16 Ceramic coatings ...................................................................................... 17

Thesis aims and objectives ............................................................................ 18

Materials ....................................................................................................... 19 Coating deposition .................................................................................... 19 Sintering ................................................................................................... 20

Characterization methods .............................................................................. 22 Compositional analysis ............................................................................ 22 Cross-Sectional analysis ........................................................................... 22 Scanning electron microscopy (SEM) ...................................................... 23 Optical interferometry .............................................................................. 23 Coating adhesion ...................................................................................... 23 Nanoindentation ....................................................................................... 24 Wear testing .............................................................................................. 25

Summaries of the studies included in thesis ................................................. 27

Paper I - Towards Functional Silicon Nitride Coatings for Joint Replacements ................................................................................................ 28

Paper II - The effect of coating density on functional properties of SiNx coated implants ............................................................................................. 30

Paper III - The effect of C, Cr and Nb content on the wear resistance of silicon nitride coatings in a hard-on-soft contact .......................................... 32

Paper IV - Morphology and dissolution rate of wear debris from silicon nitride coatings .............................................................................................. 34

Paper V - Wear performance of a new biocompatible silicon nitride for joint implant applications .............................................................................. 36

Discussion ..................................................................................................... 38

Summary and Conclusions ........................................................................... 40

Future perspectives ....................................................................................... 42

Svensk sammanfattning ................................................................................ 43

Acknowledgements ....................................................................................... 45

References ..................................................................................................... 48

Abbreviations

Al2O3 Alumina CoCrMo Cobalt chromium molybdenum alloy

(Co-28Cr-6Mo) CrN Chromium nitride CVD Chemical vapor deposition DC Direct current dcMS Direct current magnetron sputtering DLC Diamond-like carbon EDS Energy-dispersive X-ray spectroscopy EDTA Ethylene–diaminetetraacetic acid solution FBS Fetal bovine serum FIB Focused ion beam HiPIMS High-power impulse magnetron sputtering ICP-AES Inductively coupled plasma atomic

emission spectroscopy ICP-MS Inductively coupled plasma mass

spectrometry Lc Critical load MC Million cycles MgO Magnesium oxide MWT Multidirectional wear tests OxZr Oxidized zirconium PVD Physical vapor deposition rHiPIMS Reactive HiPIMS (see above) RWT Reciprocal wear tests SAE 316L SAE 316L stainless steel alloy SEM Scanning electron microscopy Si3N4 Silicon nitride, bulk (stoichiometric) SiCN Silicon carbon nitride SiNx Silicon nitride coatings (amorphous) SiO2 Silicon dioxide SPS Spark plasma sintering SrO Strontium oxide TiAlV Titanium aluminum vanadium alloy

(Ti-6Al-4V) TiN Titanium nitride

TiNbN Titanium niobium nitride TiO2 Titanium dioxide TJR THR

Total joint replacement Total hip replacement

TKR Total knee replacement UBM Unbalanced Magnetron sputtering UHMWPE Ultra-high molecular weight polyethylene XLPE Cross-linked UHMWPE (see above) XPS X-ray photoelectron spectroscopy XRD X-ray diffraction Y2O3 Yttrium oxide ZrN Zirconium nitride ZrO2 Zirconia ZTA Zirconia toughened alumina

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Introduction

Total joint replacement (TJR) is a procedure commonly applied in patients who suffer with arthritic pain or after a bone fracture in the hip and knee joint area [1–5]. The success rate is more than 90 % for total hip replace-ments (THRs) and total knee replacements (TKRs) at 10 year follow-ups [6,7]. In Sweden, more than 18,000 primary total hip replacements were performed in 2017 and more than 14,000 primary knee arthroplasties in 2018 [6,7]. The number of procedures and revisions are increasing due to the age-ing population and younger patients are receiving new joints.

Joint implants can be divided into hard-on-hard bearings and hard-on-soft bearings [8], and can be a combination of several materials including poly-mers, ceramics and metals. A widely used polymeric material is the ultra-high molecular weight polyethylene (UHMWPE), and more recently also cross-linked polyethylene (XLPE) [8,9]. For ceramics, alumina (Al2O3) and zirconia toughened alumina (ZTA) have been used, and ceramic coatings such as CrN, TiN, ZrN and oxidized zirconium (OxZr) have been applied in clinical trials [10–17]. For metal alloys such as stainless steel, titanium al-loys, and cobalt chromium molybdenum (CoCrMo) are also used depending on implant component and country.

These materials have been put forward to enhance the implant lifetime and improve a patient’s quality of life, but complications following the pro-cedure are still relatively common in the long term. For example, the body reaction to debris produced during wear is believed to lead to the recorded osteolysis in up to 22 % of the cases over time [18–23], sensitivity to metal ions may develop in about 26 % [6,24–26], or – more rarely - fracture of the liner may occur in 0.01 % to 2 % [27–30] as well as in the femoral head in 0.004 % to 1.4 % of the cases [30–33].

Silicon nitride is a material that has been subject to recent research in the field, and seems to be a promising alternative due to its high biocompatibil-ity, bacteriostatic properties, slow biodegradability with release of only bio-compatible ions, high wear resistance and hardness [18,34–41]. In this thesis both silicon nitride coatings and bulk silicon nitride material were evaluated.

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Background - Joint replacements and materials used

In THR, the ball and socket structure of the joint is replaced, i.e. the femoral head and the acetabulum [42]. The joint function is provided by the combi-nation of the spherical femoral head and the acetabular cup shape [42]. This is further strengthened by ligaments, muscles and the joint capsule [42,43]. For TKR part of the femoral and tibial bones are removed and replaced by metallic femoral and tibial components, and in order to reproduce the joint function a plastic bearing is used in between [21]. Figure 1 illustrates an unhealthy hip and knee joint and their following THR and TKR.

In the 1950s, the first modern low friction total hip replacement was per-formed by Sir John Charley. This consisted of a metal alloy and a high den-sity polyethylene for the femoral head and acetabulum, respectively, as well as a metal stem fixed by bone cement [8,44]. In TKR in the 1970s a Total Condylar Replacement was performed, based on the replacement of the tibial and femoral bearing surfaces by artificial components which were not con-nected [45]. The concept introduced by those authors is still in use today, but applied with different, newly designed materials.

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Figure 1. Radiography of an osteoarthritic hip and knee joint structures (a and c) also (b) an uncemented THR with a hard-on-hard contact and (d) a TKR with metal and polymeric components. Modified and Reprinted from King and Phillips with permission [21].

Metal alloys The biomedical alloys that are being widely used for joint applications are made of titanium alloys, stainless steel, and cobalt chromium alloys. A pas-sive layer of TiO2 forms immediately on titanium in contact with air, which is beneficial for biocompatibility and corrosion resistance [46]. The most commonly used titanium alloy is Ti-6Al-4V (TiAlV), which is used for im-plant parts which require osseointegration but not extensive wear resistance, e.g. hip stems and the tibial part of knee implants [47].

Stainless steel, namely SAE 316L, was initially used for joint implants but due to the lower corrosion resistance other materials are nowadays usual-ly used instead [47,48]. Cobalt chromium alloys and especially CoCrMo are commonly applied in joint applications due to good biocompatibility and excellent corrosion and wear resistance [49,50]. However, metal ion release and detrimental reactions to metal wear debris can occur [47].

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Polyethylene A “soft” material used in bearing couples and tibial liners that is generally applied is UHMWPE. This material has been investigated for many years but still has limitations in terms of a potential negative body response to wear debris via osteolysis and aseptic loosening [51]. Debris in a sub-micron range can accumulate in the region surrounding the implant and cause bone loss which results in implant loosening and failure. An alternative to reduce the wear debris generation was clinically introduced in the 1990’s through a cross-linked UHMWPE (XLPE), which is more wear resistant and produces less wear particles [52,53].

Ceramics Materials that offer lower-friction surfaces and reduced wear rates when compared to CoCrMo are ceramics [54–56]. Zirconia (ZrO2) and alumina (Al2O3) have been widely used for over 30 years, but may have some draw-backs. Catastrophic failures have been reported for ZrO2 [57,58] and Al2O3 [59,60] in some cases. In an attempt to avoid it composites of ZrO2 and Al2O3, i.e. Zirconia-toughened alumina (ZTA), have been used and shown promising results. However, ZrO2 phase transformation can occur in vivo [61–64].

Silicon Nitride (Si3N4) has recently emerged as a potential ceramic alter-native for joint implants. This material was initially used in blast furnaces but is now being applied in several fields of industry as bearings, cutting tools, spark plugs and turbine blades [65,66]. As a biomaterial, it was intro-duced in spinal applications in 2008 [67], and was later considered as a fem-oral head implant [8]. Biocompatibility, toughness, wear resistance, and low coefficient of friction are advantages this ceramic can offer [68–75]. Fur-thermore, it has been found to have bacteriostatic properties [66,70,73,76–80] and potential wear debris may dissolve [77].

Bulk Si3N4 can be obtained by a sintering process using sintering addi-tives such as Y2O3 and Al2O3. This can improve properties such as densifica-tion, resistance to oxidation, fracture toughness and creep resistance [41,65,66,81,82]. Recent work in our group has found that the use of SrO, MgO, and SiO2 as sintering additives are beneficial to osseointegration and cell adhesion [83–87]. Indirect cell studies have shown no toxicity [40,41] by using the additives SrO and MgO. SrO and MgO may further improve osteogenesis and vasculogenesis [41,88]. Sr may trigger osteoblast formation and hinder osteoclasts [41,89,90], and Si may improve bone mineralization [89].

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Ceramic coatings An alternative to bulk ceramics are ceramic coatings on metal. This may be beneficial for joint applications due to the heightened toughness of the me-tallic substrate, superior hardness of the ceramic coating including less wear particles as well as a reduced metal ion release from the metallic substrate [91]. The relative match with the elastic properties of the substrate and the chemical bond between layers predict the success of a coating [92]. Coatings applied in bearing surfaces that have been used clinically are TiN, DLC, ZrN, TiNbN. Oxidised zirconium (consisting of a surface modification of ceramic oxide surface of ZrO2 layer grown on a ZrNb based alloy), has also been evaluated [14,91,93–96].

Silicon nitride coatings (SiNx) have been extensively investigated in our research group. These can be deposited by physical vapor deposition (PVD) or chemical vapor deposition (CVD) techniques [34,77,97–99]. The resulting coating is usually amorphous or nano-crystalline [91]. The benefits of SiNx coatings are similar to those mentioned for the bulk material, but with the additional ceramic coating advantages mentioned before.

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Thesis aims and objectives

This thesis aims to further investigate the application of silicon nitride based materials for joint bearings, focusing on silicon nitride coatings, but also evaluating a recently developed bulk silicon nitride ceramic for tribological applications.

The specific aims and objectives of papers included in this thesis are as follows:

(1) to move further towards functional 3D SiNx coatings by investigating the effect of an interlayer as well as different bias voltages and substrate rotations on coating performance in terms of adhesion and hard-on-hard wear resistance (Paper I);

(2) to investigate the effect of coating density on its long-term perfor-mance in terms of adhesion and wear resistance in a hard-on-soft contact (Paper II);

(3) to investigate the effect of additional alloying elements and ion energy during deposition on relevant properties for SiNx coatings, with a focus on the wear resistance in a hard-on-soft contact (Paper III);

(4) to estimate the dissolution rate, shape and size of SiNx coating wear debris (Paper IV);

(5) to evaluate the wear performance of a new, biocompatible bulk Si3N4 bioceramic for future joint applications (Paper V).

The five papers are summarized in the subsequent sections, followed by some concluding remarks and notes on future perspectives.

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Materials

Coating deposition Techniques that are commonly applied to deposit ceramic coatings are chemical vapor deposition and physical vapor deposition. CVD occurs by chemical reactions of reactant gases introduced in an activated environment under heat, gas or plasma near to a heated surface, forming powders or films [100]. In PVD processes, source materials (targets) are used to deposit ions by evaporation or sputtering [101]. Coatings are deposited under vacuum by condensation of ions or molecules. An inert gas, usually argon, is heated until it reaches the plasma state. A collision of these ions with the target then allows material liberation from the target which are orientated to the desired substrate by an applied voltage [101]. During deposition a technique named reactive sputtering can be applied to deposit coatings using a reactive gas, e.g O, N, NH3, CH4, C2H2, mixed with an inert working gas [102]. The pro-cess has limitations as the substrate is heated to high temperatures, which could interfere with the coating growth whereby the plasma efficiency de-creases and the rate of deposition is lowered [103].

In Figure 2, a schematic of a magnetron sputtering process is shown. First, a magnetic field is applied parallel to the target surface resulting in a dense plasma in the target region. This increases the probability of electrons and atoms to collide [102]. The ion bombardment flux on the target is high, resulting in high deposition rates. The plasma surrounds the target region, and if the substrate is placed far apart from the plasma density, deposition rates are low [103]. For Unbalanced Magnetron sputtering (UBM) the mag-nets are placed in a region further from the substrate creating an expansion of the plasma region causing the entrapment of more electrons, which will lead to more collisions and higher ion bombardment to the substrate [103].

Direct current magnetron sputtering (dcMS) and High-power impulse magnetron sputtering (HiPIMS) differ in terms of the current applied to the target(s). In dcMS the target current is constant but in HiPIMS high power impulses are applied in a magnitude of kW compared to basic magnetron sputtering which ranges in the order of W. Pulses with durations ranging from 5 to 5000 µs at a frequency from 10 Hz to 10 kHz result in peak target

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current density and total ion flux 3 orders of magnitude higher than dcMS [104,105].

In this work dcMS was used in Paper I to deposit a CrN interlayer onto CoCrMo discs followed by rHiPIMS to deposit the SiNx top layer. In Paper II both the CrN interlayer as well as SiNx and SiCN top layers were deposit-ed by rHiPIMS. In Paper III UBM was used to apply the alloying elements Cr and Nb on the top layer and HiPIMS was used to deposit the SiNx. De-tailed information on the deposition processes can be found in Papers I-III.

Figure 2. Schematic representation of a magnetron sputtering process.

Sintering To manufacture Si3N4, bulk ceramic sintering processes can be applied such as hot isostatic pressing or hot pressing [106]. However, to obtain a Si3N4 ceramic, the sintering times can reach hours [41]. One alternative is spark plasma sintering (SPS) which gives a denser material by improving particle reordering and solution-diffusion-precipitation, reducing the sintering time from hours to minutes [107–110].

SPS is constituted of a vacuum chamber cooled by water, a single axial pressure applied in the vertical direction and electronic controllers as well as a DC pulse generator [111]. The current passes through the material to be sintered as well as the graphite die and the heating rate can be 1000 ºC/min.

Crystalline Si3N4 ceramic is composed by two phases - α trigonal and β hexagonal [112]. When the phase transformation occurs, a lattice reconstruc-tion is needed where the most unstable form, which has higher solubility, goes into solution and the more stable form precipitates which grows and

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form the mentioned grains. In the Si3N4 powder mainly α phase is present which transforms into β at temperatures higher than 1400 ºC [113].

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Characterization methods

Compositional analysis The chemical composition of the coatings was analyzed by X-ray photoelec-tron spectroscopy (XPS), which is a common technique used to investigate bonding structure and chemical composition of surfaces [114]. X-rays are bombarded onto the material surface, and when the incident photon energy is higher than the binding energy electrons of a consitutent atom, the electrons are ionized and escape from the surface. By detecting the electron kinetic energy of the ionized electrons, the binding energy can be calculated [115]. The penetration depth is in the nanometer range due to the interaction with the atoms on the surface by elastic and inelastic mechanisms [115,116]. This technique was used to analyze material composition in Papers I, II and III.

Cross-Sectional analysis The focused ion beam (FIB) is an imaging and nanostructuring instrument, which consists of an ion beam that can be focused on the sample surface with a typical beam diameter in the range between 5 nm and a few 10 nm. The FIB instrument often contains a second column, being a scanning elec-tron microscope. The materials are hit by energetic ions from a Ga+ source and when the binding energy is surpassed those atoms will be sputtered [117]. Patterns can be applied to remove the material desired geometry, i.e. the Ga ion beam can be scanned to remove specific areas. In this thesis cross-sectional analyses were performed by FIB milling to visualize the coating layers and interlayers. In the FIB instrument, it is also possible to protect areas of interest from beam damage via localized coating depositions, for example by using Pt. This technique uses the local decomposition of precursor gases under the focused ion or electron beam and is called ion or electron beam induced deposition, respectively. The FIB technique was used to analyze coatings cross-sections in Papers I and II.

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Scanning electron microscopy (SEM) SEM is used when topographic information from the surface is desired. The primary signal that is used to obtain an image in the SEM consists in sec-ondary electrons (SE) emitted from the sample surface, when the primary electron interacts with the electronic shell of the atom. The SEM images provide information about topography as well as of surface layers. When the sample surface has strong height levels, the high depth of focus of the SEM can be used to obtain images that are well focused at every point of the sam-ple compared to an optical microscope which has a low depth of focus [118]. To obtain an image in the SEM, the focused electron beam is scanned along surface and the signals resulting from the interaction between the electrons and the sample are reported scan-point by scan-point on the screen, leading to a resolution of the SEM images between sub-nanometer and a few na-nometers depending on the nature of the imaged object [118]. This technique was used to analyze surface morphology and carry out a particle analysis in Papers I, II, IV and V.

Optical interferometry White-light interferometry is used to give an accurate optical measurement of the contour of objects [119]. A beam of light generated by the microscope will be divided in two: the object beam and the reference beam which will be reflected by a reference mirror [120]. The objective beam is modulated from the alteration of the height of the analyzed material, a camera records each frame resulting in interferograms of each pixel for later reconstruction by signal processing to obtain the material topography [120]. This technique was used to analyze surface roughness and wear tracks from RWT in Papers I, II, III and V.

Coating adhesion Coating adherence to the substrate can be estimated by Rockwell indentors and can be done by quasi-static loading in single points or by progressive loading and horizontal displacement, i.e. a scratch test. When indentations are used, the damaged area of the coating surrounding the indentation is analyzed by an optical microscope to investigate for cracks and/or flaking [121]. In Table 1 the description of the standard classification for the adhe-sion as measured by the indentations can be seen as well as the schematic representation of the coatings failures in Figure 3.

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When applying the scratch test, the failure of the coating is analyzed by optical microscopy. The force applied when the coating fails in some way is named critical load Lc [122]. The coating cracking usually happens at lower loads and this critical load is named Lc1, coating detachment Lc2 and the number of nth failure modes is defined by Lcn. This technique was used to analyze coating adhesion in Papers I, II and III.

Table 1. Description of the indentations analyzed by optical microscope to evaluate adhesion properties. Modified from ISO 26443:2008.

Classification Indentation description

Class 0 No visible cracking or adhesive delamination

Class 1 Cracking occurs but no adhesive delamina-tion can be seen

Class 2 There is no cracking but adhesive delamina-tion partially occurs

Class 3 Adhesive delamination completely occurs

Figure 3. Schematic representation of the coating failures by critical normal loads (1) and isolated event during scratch test (2). Modified and reprinted from ISO 20502:2005 [122].

Nanoindentation Nanoindentation is commonly applied to measure mechanical properties such as the Young’s modulus (E) and hardness (H) at the nanometer scale. The applied load and displacement are measured and combined with the indentation depth, the mechanical properties are estimated [123].

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Nanoindentation results are usually presented in a load-displacement curve which shows the elastic and plastic deformation for the loading curve and the elastic recovery for the unloading curve [124]. The Hardness (H) is cal-culated as the maximum indentation load (Pmax) divided by the projected area (A) of the impression [125]. To calculate the Young’s modulus, the Oliver and Pharr method [126] can be used when the Poisson’s ratio is known [124,125]. This technique was used to analyze mechanical properties in Paper III.

Wear testing To simulate the in vivo conditions several different types of wear tests have been applied. Compared to the actual implementation of these tests, our ex-periments are simplifications but can still give a reasonable preliminary evaluation of the materials performance. In Figure 4 the two types of wear tests performed in this thesis are illustrated, i.e. reciprocal wear tests (RWT) and multidirectional wear tests (MWT), based on a ball-on-disc and pin-on-disk setup, respectively. In the RWT a hard-on-hard and hard-on-soft contact was used, and in the MWT a hard-on-soft contact. Tests were carried out for thousands to millions of cycles under 37 ºC and lubricated conditions of simulated body fluid. In RWT the Hertzian contact pressure for the hard-on-soft contact was 9 MPa, which is the estimated contact pressure for a hard-on-soft contact in a hip implant [127]. In the hard-on-hard contact pressures of approximately 328 MPa, 442 MPa and 700 MPa were used. The worst case scenario of an edge loading condition by microseparation in a contact of ceramic-on-metal is approximately 700 MPa [128]. In MWT the adopted contact pressure was 3 MPa, which according to Saikko et al. is the contact pressure needed to obtain wear similar to what has been found in clinical data [129]. The wear rate was calculated from the cross sectional area of wear tracks in RWT based on Archard’s wear equation [130]. In the MWT, the volumetric wear was obtained for calculation of the wear factor, which is defined by the volumetric wear divided by the applied load multiplied by the sliding distance [131]. The coefficient of friction and wear rate of the mate-rials were assessed in relation to commonly used materials. This technique was used to analyze the coefficient of friction and wear in Papers I, II and III and V.

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Figure 4. Schematic representation of multidirectional pin-on-disc (left) and recip-rocal ball-on-disc (right) set-up used for wear testing. Dotted line describes the movement direction of wear path on the material.

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Summaries of the studies included in thesis

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Paper I - Towards Functional Silicon Nitride Coatings for Joint Replacements

The aim of this study was to investigate the SiNx coatings deposited on Co-CoCrMo with a CrN interlayer employing different substrate fold rotation and bias voltage.

To this end, the microstructure, surface roughness, coating adhesion and wear resistance were investigated by the effect of different bias voltages and substrate rotation (1-fold and 3-fold rotation) applied during the deposition process. The effect of a CrN interlayer was also evaluated, with the aim to improve adhesion.

A reciprocal ball-on-disk set-up was used, sliding Si3N4 balls against CoCrMo alloy discs coated with a SiNx top layer by reactive high-power impulse magnetron sputtering (rHiPIMS). Uncoated material was used as control. The wear tests were performed using a 10 mm and 20 mm Si3N4 ball and contact pressures of 328 MPa (20 mm ball), 442 MPa (20 mm ball) and 700 MPa (10 mm ball), where the worst case scenario aimed at replicating an edge loading condition having a contact pressure of 700 MPa [128]. A frequency of 1 Hz was used during 1x10+4 cycles. In all wear tests, 25 vol.% fetal bovine serum, with 0.075 wt.% sodium azide and 20.0 mM ethylene–diaminetetraacetic acid solution (EDTA) was used, according to the standard [132].

As can be seen in Figure 5, depositions with 1-fold rotation showed no columnar structures and a denser, more uniform coatings is obsereved when compared to 3-fold rotation, due to a higher particle arrival rate and higher energy during coating growth [133–135].

The N/Si ratio of the coatings (1.1-1.25) were compared to previous stud-ies [35] and concluded to likely be favorable for reducing the dissolution rate resulting in enhanced mechanical properties due to an increased Si-N bonds [136]. The surface roughness of the coatings ranged between 16 - 23 nm and was comparable to previous work. This fulfilled the biomedical standards for wearing surfaces [137,138].

The introduction of a CrN interlayer enhanced the coating adhesion. Coat-ing adhesion could be compared to previous work of coatings that are being clinically in use such as TiN and ZrN [10,139]. 3-fold rotation also gave a

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better adhesion, probably related to the lower coating density and less resid-ual stresses [140–142]. The coefficient of friction obtained, ranging between 0.33-0.42, was similar to other hard-on-hard contacts, e.g. ceramic-on ce-ramic [143]. Specific wear rates found were higher when compared to simi-lar coatings except for uncoated CoCrMo against Si3N4 balls at contact pres-sures of 328 MPa and 442 MPa [34,39]. This can be due to coating mor-phology, density as well as differences in set-ups, and it is difficult to make direct comparisons [34,39,144–147].

However, none of the coatings in this study wore through to the interlayer or substrate. Coatings with lower bias voltages and 3-fold rotation showed a low specific wear rate compared to CoCrMo control. However, the tests used were relatively short, and longer tests in set-ups more similar to the in vivo conditions were concluded to be the next step.

Figure 5. Cross-sections of (a) SiNx coating, without CrN interlayer, a dense coating could be observed; (b) SiNx coating, deposited using 1-fold rotation and higher bias voltage; (c) SiNx coating, with 1-fold rotation and lower bias voltage; and (d) SiNx coating, deposited using 3-fold rotation and lower bias voltage. Reprinted with permission from Paper I [148].

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Paper II - The effect of coating density on functional properties of SiNx coated implants

After the encouraging results in Paper I, and the evaluation of coating micro-structure, chemical composition, surface roughness, coating adhesion and preliminary wear resistance, in this work silicon nitride coatings were char-acterized in terms of adhesion and density over time by soaking 2D coatings in fetal bovine serum (FBS) solution for 1, 3 and 6 weeks, and evaluated at these time points through scratch tests and cross-sections by focused ion beam (FIB). The coating composition was evaluated by X-ray photoelectron spectroscopy (XPS) and the wear performance by reciprocal wear tests on coated full head implants (3D) at 37 °C in FBS solution against UHMWPE discs.

According to previous work, coatings with a stoichiometry N/Si ratio larger than1.1 performs better in dissolution tests. This is likely related to high binding energies of Si-N bonds [35,149]. In this work, a N/Si ratio ranging between 0.8-1.0 was found, and some of the coatings failed after longer exposure to the lubricant solution. In paper I the coatings with 1-fold rotation had denser structures due to more exposition to the cathodes and receiving higher ad-atom flux of film deposition [97]. Here, 2D coatings with 1-fold rotation and higher Si target power indeed showed denser struc-tures compared to the 3D coatings, seen in Figure 6 and Figure 7, due to the rotation process giving less dense coatings leading to more attachment of O and C after exposure to air [136]. With an increase in N content and Si target power denser coatings could be produced.

The lower performance in scratch tests over time for one of the coatings with 1-fold rotation, process heating of 0 kW and average target power of 3.4 kW could be related to the higher O content which was very similar to 3D coatings with no C content, lower target power and process heating re-sulting in coatings that were less dense with a higher dissolution rate.

The coefficient of friction for coated and uncoated materials running against UHMWPE showed a similar order of magnitude. Full head coated implants gave similar wear rates of the UHMWPE as compared to the un-coated control, as well as to earlier studies, although for one coating a statis-tically significantly higher wear rate was found [150–152]. This could be

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related to the higher surface roughness of that coating. The findings in this paper showed promising result for SiNx coatings, however further investiga-tion in full head implants is needed.

Figure 6. Cross sections from full head implant coated with SiNx, 3-fold substrate rotation, heating process of 0 kW and average target power of 1.7 kW before (a) and after (b) reciprocal wear test, showing surface morphology and coating layer cross sections. Reprinted with permission from Paper II [153].

Figure 7. Cross sectional image of a full head implant coated with SiNx, 3-fold sub-strate rotation, heating process of 3 kW and average target power of 3.4 kW before (a) and after (b) reciprocal wear test, showing surface morphology and coating layer cross sections. Reprinted with permission from Paper II [153].

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Paper III - The effect of C, Cr and Nb content on the wear resistance of silicon nitride coatings in a hard-on-soft contact

SiNx coatings in Paper II presented potential results for joint applications with some presenting a good adhesion, chemical stability and good wear performance in a hard-on-soft contact. Paper III aimed to investigate the influence of alloying elements N, Cr and Nb deposited by high power im-pulse magnetron sputtering and unbalanced magnetron sputtering using 2-fold substrate rotation and low, medium and high voltages. This was applied to improve mechanical properties or/and chemical stability for the tribocor-rosive performance. After deposition the coatings were characterized by compositional analysis using X-ray photoelectron spectroscopy, the surface roughness was evaluated by optical profilometry, mechanical properties characterized by nanoindentation, coating adhesion measured by scratch testing, and wear resistance tested under fetal bovine solution at 37 °C by multidirectional wear tests against UHMWPE pins.

Coating thickness ranged from 3.7 - 8.8 µm and the surface roughness reached was below 50 nm, fulfilling the standard [154]. The hardness ranged between 13 – 28.4 GPa and Young’s modulus from 152 – 286.3 GPa, being similar to previous work [34,39,99,155]. Adhesion tests showed higher Lc2 values for coatings with higher O and Cr content, i.e. less dense coatings having less residual stresses. During wear tests, the formation of a white layer on some of the coatings’ surface occurred. After analysis by XPS it was suggested that this could be due to a tribochemical reaction of Si3N4 in wet conditions and the presence of SiO2 and Si(OH)2 layer on the surface. Coatings with lower N content and higher O content presented a surface reaction and/or coating dissolution during wear tests. In Figure 8 can be observed that coatings with no or relatively low presence of O (except a coating with Cr which had 4 at% of O), survived to 2 million cycles of wear and presented a low volumetric wear rate of UHMWPE pins. Coatings with a higher N content and a lower O content may therefore be related to denser coatings with less reactivity which is desired for joint applications.

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Figure 8. Typical macroscopic appearances of a) a reacted surface (control coat-ing), b) failed coating containing Nb; and coatings that did not fail after 2 M cycles but in which a surface layer could be observed forming, c) coating with Cr content and d) coating with higher Si target power of 8 kW. In e) a high bias voltage coating is shown, which did not present any layer formation or upcoming failure up to 2 MC. Reprinted with permission from Paper III.

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Paper IV - Morphology and dissolution rate of wear debris from silicon nitride coatings

While a coating with as low dissolution rate as possible is desired, rapid dissolution of any wear debris would be beneficial. In this work, wear debris from SiNx coatings was generated with a reciprocal ball-on-disc set-up to investigate their shape and size for future research in in vitro and in vivo studies. Due to the difficulty in producing large amounts of wear particles, commercial model particles were then used to evaluate the dissolution rate.

An Al2O3 ball was sled with a contact pressure of 0.41 GPa against SiNx coatings. The SiNx coatings were deposited onto CoCrMo alloy discs (ASTM F-75) by rHiPIMS similar to earlier work [35,39,97] and with a N/Si ratio of 0.8. UHMWPE (GUR 1050) discs were also used for particle gen-eration of control material. The particle digestion protocol followed the work of Scott et al. and standard ISO 17853:2011 procedures [156,157]. To char-acterize the particles, two separate methods were used, a screening with a tabletop SEM at 15 kV and backscatter detector both with no conductive layer. After image acquisition a modified MATLAB script was applied, adapted from Gontard et al. [158]. Secondly, a high-resolution method was used, where particle solutions were dried in a polycarbonate filter membrane of 0.1 µm and sputtered with Ag/Pd for conductivity. A field emission gun SEM with in-lens detector set to 5 kV as well as an energy-dispersive X-ray spectroscopy (EDS) detector were used. EDS was used to discriminate be-tween SiNx and UHMWPE particles, debris from Al2O3, proteins and salts. Software analysis was performed using GIMP 2.6 for particle size measure-ment. For the dissolution study of model particles, a simulated body fluid was used. Particles in aqueous solutions at a concentration of 100 mg/L were used, with time points ranging from 0 - 30 days. The pH was measured throughout and ICP-MS analysis was used for concentrations below 250 mg/L and ICP-AES for concentrations above 250 mg/L.

It was found that the UHMWPE debris had a fibril shape ranging from 0.11 - 7.2 µm and mean size of 0.29 µm being similar to previous work. It is shown in Figure 9 and Figure 10. The SiNx debris were round with mean size of 40 nm and ranging from 10 - 500 nm, but agglomerated to sizes up to 3.2 µm with mean size of 0.59 nm. Both UHMWPE and SiNx debris were in

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the critical range for macrophage activation [159]. Dissolution tests showed that the dissolution rate found was higher than the estimated wear rate of ceramic hip implants.

Figure 9. (A, B) High-resolution of SiNx wear debris agglomerates in the submi-crometer to micrometer range. (C) Individual debris in the nanometer range can be observed in more detail. Reprinted with permission from Paper IV [160].

Figure 10. (A) Model SiNx particles, with similar size and morphology to the wear debris. (B) Zoom in of particles agglomeration. Reprinted with permission from Paper IV [160].

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Paper V - Wear performance of a new biocompatible silicon nitride for joint implant applications

In this thesis in Papers I-IV the density, morphology, dissolution, mechani-cal properties, wear resistance and adhesion of SiNx coatings were investi-gated. This final Paper V aims to evaluate the wear performance of a new biocompatible bulk silicon nitride for joint applications. The material used in this work was sintered by spark plasma sintering (SPS), from Si3N4 raw powder mixed with sintering additives SrO, MgO and SiO2 resulting in 2%SiO2-4%MgO-4% SrO-90%Si3N4 (-phase, wt%) and 2%SiO2-8%MgO-8%SrO-82%Si3N4 (-phase, wt%). This material has earlier been developed at the Division, as a fully biocompatible alternative to the currently used com-mercial material in the market, 4%Al2O3–6%Y2O3–90%Si3N4, which was used as a control. This would hence permit the usage of a material without alumina and yttria, and instead use materials known to have beneficial ef-fects to bones [41,88–90].

The surface roughness was characterized by optical profilometry and sur-face morphology by scanning electron microscopy (SEM). The phase quanti-fication and identification was determined by X-ray diffraction (XRD), and wear resistance by multidirectional wear tests against UHMWPE pins under fetal bovine solution as a wear lubricant until 2 million cycles (MC). At a time point of 0.5 MC, each sample was cleaned and dried for gravimetric analysis of the UHMWPE pins. The pH was also measured by a pH meter.

It was found that the surface roughness after grinding and polishing ful-filled the standard of below 50 nm for ceramics [154], besides the control material which was slightly higher on average (5%). During the wear tests the surface roughness of some of the new Si3N4 materials decreased to below 25 nm and for UHMWPE pins the roughness was below 2 µm after the wear tests. The material porosity increased during wear tests as shown in Figure 11. This is due to the glass phase slowly dissolving and exposing Si3N4 grains. The surface of the UHMWPE pins presented deformities and material removal during wear tests. The repetitive cycles deforms the polymer, and the UHMWPE macromolecules are reoriented in the main sliding direction giving rise to strain hardening [131,132,161–166]. A low coefficient of fric-

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tion and lower or similar wear factors were found comparable to previous work as well as compared to acetabular cups extracted from patients [131,167–170]. These results highlight the promise of Si3N4 for joint bearing applications.

Figure 11. SEM images from sintered bulk Si3N4. A-c) Si3N4 before MWT at 3500x magnification. D-f after MWT (2 MC) at 10000x magnification and g-i)materials etched with HF at 20000x magnification. Reprinted with permission from Paper V.

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Discussion

The background to this thesis lies in the hypothesis that a wear resistant, biocompatible, load bearing, bacteriostatic, slowly resorbable material could be an optimal joint replacement material. A potential target profile for a fu-ture product based on such technology would include bench studies and both preclinical and clinical studies as proof of concept. In this thesis, silicon nitride has been proposed as a material to meet the material profile. Key tests to develop understanding and first proof of the material potential has been performed [34,35,40,41,77,153,160,171], e.g. dissolution rate tests, wear performance characterization and preclinical testing. The results are promis-ing, however show that either a relatively thick coating on metals or a high-quality bulk ceramic material (i.e. high toughness) are necessary to reach a target profile for clinical use. The papers included in this thesis investigated the influence of deposition parameters on surface roughness, coating adhe-sion, coating density, coefficient of friction, wear and mechanical properties of SiNx coatings. Furthermore, coating debris generated from wear tests was characterized and its dissolution rate estimated using model particles. The wear performance of a new, sintered bulk Si3N4 bioceramic was also investi-gated.

In paper I the influence of substrate rotation on the coating density and adhesion was investigated, where a lower ad-atom flux and lower deposition energies led to lower densities for increased rotation [97,172,173], resulting in coatings with less residual stress and higher surface roughness. Coatings with lower bias voltages and 3-fold rotation however showed a low specific wear rate compared to CoCrMo control in short, reciprocal wear tests against bulk Si3N4 balls.

After the results from paper I, the aim of paper II was to investigate the coating density over time as well as in a tribological hard-on-soft contact against UHMWPE for 2D and 3D substrates. It was found again the sub-strate rotation influenced N/Si ratio, coating density and surface roughness Coatings with higher target power and higher process heating presented bet-ter results probably due more deposition rate even though 3D substrate showed less denser coatings. The presence of a CrN interlayer improved coating adhesion, showing similar values to coatings that are being used clinically [10,139,141].

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In paper III the influence of the addition of alloying elements was investi-gated in terms of coating density and reactivity. It was found that the pres-ence of higher concentrations of impurities gave a lower density and that the N content influenced coating dissolution, adhesion as well as wear rates. In brief, the presence of more Si-O bonds [35,149] than Si-N bonds was detri-mental [149]. The target power in coating deposition is an important parame-ter as it influences the resulting performance in terms of coating density.

In paper IV it was shown that agglomeration occurred for silicon nitride wear particles, from nano to micron scale range. It is reasonable to assume that agglomeration can start during the wear process. Dissolution of wear particles was estimated to occur at a higher rate than their generation.

In paper V the wear performance of new Si3N4 bioceramics containing only biocompatible additives was evaluated. The surface roughness of the control material increased during the wear tests while for the material with new additives the results were more stable, despite some dissolution occur-ring also here during FBS exposure [40,41]. Wear properties showed prom-ising results in terms of coefficient of friction and wear being comparable to bearings extracted from real patients and also from simulation studies. The dissolution of the material may however be a concern for the future applica-tion.

In general the developed coatings and bulk material reached the require-ments of the biomedical standard for surface roughness [174]. During the wear tests the surface was essentially polished, and showed a stable behavior similar to what is found in hip joint simulators [175,176].

The coefficient of friction found was comparable to previous work con-sidering both wear test setups applied in this thesis. Surface roughness re-sults were closely connected to the ones for the coefficient of friction, as expected.

Wear resistance of UHMWPE for 2D and 3D substrates showed promis-ing results which were compared to previous work for coatings and bulk materials [131,167–170]. The deposition method applied was reasonable but tuning the deposition parameters is likely still necessary to repeatedly achieve dense, stable coatings on three-dimensional objects.

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Summary and Conclusions

The increasing numbers of THRs and TKRs as well as surgical revisions requires further development of current and new materials to give the pa-tients a better life quality. Current materials have some limitations and the body reaction to the debris generated during wear process is one of the main concerns of these procedures. The focus of this work was to evaluate the potential of silicon nitride based materials for joint applications.

This thesis has investigated and discussed several properties of SiNx coat-ings, namely wear resistance, coating adhesion, surface roughness, coating structure and chemical composition. In the bulk Si3N4 wear resistance, sur-face morphology, surface roughness and identification of crystallographic phases were investigated. A brief summary and main conclusions of each paper are listed below:

(1) The obtained coefficient of friction in a reciprocal wear test of a hard-on-hard contact was comparable to other studies in a ceramic-on-ceramic contact. Coatings deposited with a low bias voltage and 3-fold rotation pre-sented low specific wear rates when compared to CoCrMo alloy used as a control. A CrN interlayer improved the coating adhesion to the substrate.

(2) Coatings deposited with 3-fold rotation sometimes showed inadequate density as compared to coatings deposited with 1-fold rotation, leading to dissolution and premature failure. When the N content and Si target power increased denser coatings were obtained. 3D coatings and uncoated materials presented a coefficient of friction in the same order of magnitude. The spe-cific wear rate for 32 mm and 36 mm coated implant heads was similar to uncoated heads.

(3) Coatings with higher O and Cr content presented higher critical load in scratch tests, as a result from lower residual stresses and less dense coat-ings. A layer formation on the top of some of the tested coatings was found to be related to the tribochemical reaction of silicon nitride in aqueous envi-ronment resulting in the presence of SiO2 and Si(OH)2 on the exposed area. Coatings with lower N content and high O content showed higher dissolution rate in the tribocorrosive tests. Coatings with no or lower O content except for the coating with higher Cr content survived the multidirectional wear tests. Dense and less reactive coatings are required for bearing applications.

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(4) SiNx debris had round shape and ranged from 100 - 500 nm with a mean size of 40 nm. Control UHMWPE debris had fibril-shape and ranged from 0.11 - 7.2 µm with a mean size of 0.29 µm in accordance with previous studies and what is found in vivo. The agglomerates of SiNx and UHMWPE particles were in the critical macrophage activation range. The dissolution tests of SiNx particles presented a higher dissolution rate compared to the estimated wear rate from ceramic hip implants.

(5) The surface porosity of the bulk Si3N4 bioceramics increased during the multidirectional wear tests against UHMWPE pins, but no debris could be found attached to the surface of Si3N4. The coefficient of friction and specific wear rate were similar or lower compared to previous work on coat-ings and bulk materials, being a promising result for bearing applications, despite the dissolution being a potential concern.

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Future perspectives

Ceramic coatings, and silicon nitride in particular, may be an alternative to reduce metal ion release and negative body reactions to debris from wear of joint implants. The findings in this thesis demonstrated some advantages and some limitations in the possible application of silicon nitride based coatings and bulk materials for joint bearing applications. However, further investiga-tion is still necessary for these materials. In particular, the following future directions are suggested:

• Further coating development to produce coatings with higher density and higher chemical stability to minimize tribocorrosion;

• Longer wear tests to evaluate long-term wear resistance of SiNx coatings;

• Wear tests more similar to in vivo conditions using SiNx coatings and bulk Si3N4, in e.g. joint simulators.

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Svensk sammanfattning

Höft- och knäledsoperationer har utförts framgångsrikt i flera decennier. I dessa ersätts en del av den ursprungliga vävnaden med implantat som kan vara tillverkade av keramer, polymerer eller metaller. Trots stora framgångar uppvisar dessa material fortfarande en del nackdelar. Dessa är främst relate-rade till hur kroppen reagerar på dessa material, och framför allt de små par-tiklar som alstras när materialen glider mot varandra. Negativa reaktioner på grund av överkänslighet för den insatta metallen förekommer också. Detta är en anledning till en konstant pågående jakt efter nya material. I den här av-handlingen föreslås ett material med namnet kiselnitrid, vilket har flera egenskaper som är önskvärda, såsom biokompatibilitet, högt nötningsmot-stånd samt biologisk nedbrytbarhet, dvs. nötningspartiklar som kan absorbe-ras av kroppen. Vid exponering i vattenhaltig miljö inträffar en tribokemisk reaktion och det kan bildas ett skikt av kiseloxid och kiselhydroxid på materialytan, vilket är fördelaktigt då det minskar friktionskoefficienten och slitaget. När materialet används som beläggning på en metall så minskar frisättningen av metalljoner. I den här avhandlingen har fokus lagts på kisel-nitrid i form av tunna beläggningar.

Undersökningarna har visat att hur underlaget roteras under beläggnings-processen påverkar skiktets densitet och ytmorfologi. Dessutom är tillsatsen av ett mellanlager av kromnitrid mellan substrat och kiselnitridskikt fördel-aktigt för vidhäftningen. Beläggningar med ökad substratrotation, benämnd 3-faldig rotation, var svårare att få täta och löstes ofta upp för snabbt i ned-brytnings- och nötningstester. Kvävehalten i beläggningen och den pålagda effekten på källmaterialet under beläggning, i det här fallet kisel, förbättrade nötningsmotståndet och beläggningsdensiteten. Implantat med och utan beläggning uppvisade samma storleksordning på både friktionskoefficient och specifik nötningshastighet av polyeten.

Vidhäftningen av beläggningar med högre syre- och krominnehåll var högre på grund av mindre tätare beläggning med lägre restspänningar. Å andra sidan gav beläggningar med inget eller lägre syreinnehåll mycket låg nötningshastighet. Sammanfattningsvis behövs tätare och mindre reaktiva beläggningar för tillämpningen.

Partiklar av kiselnitrid och polyeten genererades i nötningstester och det kunde konstateras att deras form och storlek stämde överens med vad som

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tidigare har observerats i litteraturen. Agglomerationen av dessa partiklar låg dock inom ett kritiskt intervall för aktivering av immunsystemet. Upplös-ningstester av partiklarna visade en högre upplösningshastighet jämfört med generering av partiklar i keramiska höftimplantat, vilket ansågs lovande för en eventuell tillämpning på ledimplantat.

Slutligen så tillverkades och utvärderades en ny typ av bulk-kiselnitrid, och vid nötningstest mot polyeten var friktionskoefficienten och nötnings-hastigheten lägre än vad som tidigare observerats, och inga partiklar kunde hittas på kiselnitridytan.

Resultaten från studierna i den här avhandlingen är lovande för en fram-tida applikation av materialet i ledimplantat och andra lastbärande implantat-tillämpningar.

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Acknowledgements

First I would like to thank God for blessing me with this opportunity. A special thanks to my three supervisors Dr. Cecilia Persson for your

leadership, unlimited and extraordinary patience, guidance, unconditional support during this PhD journey and for always being positive and pushing me to the limit, Dr. Klaus Leifer for your orientation during the PhD and for giving me the opportunity of an interview 5 years ago you are one of the big responsibles of me being here in Sweden as well as Dr. Håkan Engqvist for your orientation and for giving me a different perspective about the academ-ic and industrial environment.

A special thanks for the funding of this PhD education by the European Union, grant number FP7-NMP-2012-310477 (Life Long Joints project) as well as EBW+ Project Erasmus Mundus Programme, Action 2 – STRAND 1, Lot 9 (Latin America), Brazil, Grant number 2014-0982.

I would like to thank my friends and colleagues from ElMIN group YuanYuan, Tian Bo, Hu, Omer, Ling also Hasan Ali and Ishtiaq for hours of nice conversation and help with the FIB and TEM.

From Engineering Sciences department, MIM, BMS and MSL group, Mi-chael, Shiuli, Le, Henry (Xi), Lee, Oscar, Toshiharu, David, Caroline, Wei, Ingrid, Lars, Sara R., Fredric, Jean-Åke, Ernesto, Dan, Elin, Andrea, There-za, Ioannis, Salim and Marjam. A big thanks to the Tribogroup members as well as Jonatan the wizard for resurrecting my computer several times. In-grid Ringård for being very helpful, friendly and always with a big smile when I went to her office to ask for help. Susanne and Camilla for being nice and working together in the statistics course. A special thanks to Camilla and Amina for your kindness trying to cheer me up and for the special breakfast also for the mushroom adventure day, I will never forget that. Sara Gallinetti for always being kind and always up for a big hug. Victoria for the several times helping me with SEM, for being a good person and the extraordinary help when I moved to another apartment. Anna for being a big sister here in Sweden, being nice, kind, true friend, having tons of patience and always available to help. Alejandro for the infinite help during the PhD, parties in your house, good friendship and sharing very good moments in those years. Jun thanks for being the extraordinary person that you are always smiling and happy, for introducing me to the best Chinese cake in the world the

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Moon cake. Gry and Victor for always being friendly and to bring our group to your house. Céline for being friendly and always with a big smile. Charlotte for being very helpful and for the great support working together.

A special thanks for Cristiano, Juliana, Igor, Fábio, Heiður, Marco, Petar, Leonor, Yavor, Simeon, Mailing, Débora, Filipe, Ramon, Daiane, Bruna, Rafael B1, Rafael B2, and André for being receptive, friendly and make my days here in Sweden more special. Dibya for your friendship, help with XPS and long hours of conversation about future and life in the latest years. Felipe Bahêa (Ministro) and Mirte for being very good friends, several barbecues and for been there in any moment.

Huge thanks for Maurício, Marisa, Catarina, Maria Inês and Daniele for being friendly, very receptive and for the support to me and to my mother, for what you have been doing to her I am in debt with you guys for my entire life.

A very special thanks to Ana del Pozo Cano for being a great human being, kind, friendly and for the huge support in the last years, you have a big part in this achievement. Muchas gracias !!!.

A big thanks for my Jiu-jitsu team mates here in Sweden, Nuno, Daniel, Ida, Sophia, Bert, Oliver, Jonas, Johannes and Arash always motivating and supporting me.

A special thanks para los compadres de sudamerica e amigos de Suecia Agneta, Cruzito, Tupac, Fabian, Alejandro, Felipe, Paolo, Nico, José, Rolando, Luís, Maikol, Nelson and Carlos.

A special thanks to my friends from Lato Sensu and UEA, Wellington, Gean, Edgar, Diego, Rafael, Fábio, Katriane (without your help in the application this achievement would not be possible, Thank you very much), Rubelmar Filho and Dr. Rubelmar Neto (without you I would not be able to start this journey a long time ago, Thank you my friend), Igor, Roque, André and Casemiro which have been loyal on my side after several battles during those years. Juntos até o fim rapaziada !. Also a special thanks to the friends I have made in Remanso an unique and lovely place in Manaus.

A special thanks to my professors from UEA and UNB, Dr. Arlindo (who supported and helped in the PhD application), Dr. Rogério, Dr. Gilberto and Dr. Palloma which helped, supported, pushed, and taught me countless life lesson and technical knowledge. Muito obrigado mestres sem vocês não seria possível, esta conquista é para vocês.

A special thanks to Rita Aguiar and family as well as Alencar’s family for the support, friendship, help, kindness and for adopting me as a family member this I can never forget, you have been very important during my journey. Muito obrigado por tudo !.

A huge thanks to my Jiu-Jitsu masters Ângelo e Cristiano Carioca and my team mates which taught me values of loyalty, hierarchy, discipline, team

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work, respect, self-steam, perseverance and other two important values will power and faith that we must always believe no matter what no matter how, just keep on going. NÃO HÁ VITÓRIA SEM DOR E SACRIFÍCIO and as Master Carioca told me once even though you are injured, under pain, no energies, no strength but you still have your unbreakable champion spirit go there overcome that obstacle and bring home the victory. Raçaaaaa !!!.

Now the last but not least the most important person to me in this uni-verse, the one that could sacrifice her own life to give it to me, the one who gave up her own dreams and goals in life to give the best to me and to my grandmother, the one I can really trust and always expect kindness, my best and real friend, the reason that I have been accomplishing several goals in my life, the star that guides me no matter how dark and difficult is the path. My super hero, my mom Nélcinha. Thank you from the deep of my heart and soul for everything. I am so proud, blessed and grateful for being your son. Muito obrigado mamãe !. Toda esta jornada é para você e por você !!!.

Como Racionais MC’s disseram acreditar que sonhar sempre é preciso, é o que mantém os irmãos vivos !. Tem que acreditar (You have to believe) !!!.

Figure 12. The confluence of Negro river and Solimões river near to Manaus, Brazil where the waters of both rivers are side by side for an extension of 6 km. Reprinted with permission from [177].

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2. Katz, J.N. Total joint replacement in osteoarthritis. Best Pract. Res. Clin. Rheumatol. 2006.

3. Shan, L.; Shan, B.; Graham, D.; Saxena, A. Total hip replacement: A systematic review and meta-analysis on mid-term quality of life. Osteoarthr. Cartil. 2014.

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