Gustav Sundell

Atomically resolved tissue integration

In the field of biomedical technology, a critical aspect is the ability to control and understand the integration of an implantable device in living tissue. Despite the technical advances in the development of biomaterials, the elaborate interplay encompassing materials science and biology on the atomic level is not very well understood. Within implantology, anchoring a biomaterial device into bone tissue is termed osseointegration. In the most accepted theory, osseointegration is defined as an interfacial bonding between implant and bone; however, there is lack of experimental evidence to confirm this. Here we show that atom probe tomography can be used to study the implant-tissue interaction, allowing for three-dimensional atomic mapping of the interface region. Interestingly, our analyses demonstrated that direct contact between Ca atoms and the implanted titanium oxide surface is formed without the presence of a protein interlayer, which means that a pure inorganic interface is created, hence giving experimental support to the current theory of osseointegration. We foresee that this result will be of importance in the development of future biomaterials as well as in the design of in vitro evaluation techniques.

Hydrogen analysis in APT: Methods to control adsorption and dissociation of H2

Experimental factors that influence adsorption of hydrogen from the residual gas on a nickel-rich alloy during atom probe tomography are investigated. The rate of adsorption has a maximum value at field strengths between 24 and 26 V/nm. It is found that by selecting sufficiently high laser energies, or alternatively high DC fields, it is possible to significantly reduce adsorbed quantities. Some of the physical mechanisms for hydrogen supply to the analyzed area of the tip are discussed, and it is concluded that the dominating supply mechanism is most likely direct adsorption from the gas phase. Low hydrogen adsorption at high fields is attributed to autoionization, and a decline at low fields is explained by reduced field adsorption.

The bone-implant interface of dental implants in humans on the atomic scale

Osseointegration of dental implants occurs on a hierarchy of length scales down to the atomic level. A deeper understanding of the complex processes that take place at the surface of an implant on the smallest scale is of interest for the development of improved biomaterials. To date, transmission electron microscopy (TEM) has been utilized for examination of the bone-implant interface, providing details on the nanometer level. In this study we show that TEM imaging can be complemented with atom probe tomography (APT) to reveal the chemical composition of a Ti-based dental implant in a human jaw on the atomic level of resolution. As the atom probe technique has equal sensitivity for all elements, it allows for 3 dimensional characterizations of osseointegrated interfaces with unprecedented resolution. The APT reconstructions reveal a Ca-enriched zone in the immediate vicinity of the implant surface. A surface oxide of some 5nm thickness was measured on the titanium implant, with a sub-stoichiometric composition with respect to TiO2. Minor incorporation of Ca into the thin oxide film was also evident. We conclude that the APT technique is capable of revealing chemical information from the bone-implant interface in 3D with unprecedented resolution, thus providing important insights into the mechanisms behind osseointegration. STATEMENT OF SIGNIFICANCE Osseointegration of dental implants occurs on a hierarchy of length scales down to the atomic level. A deeper understanding of the complex processes that take place at the surface of an implant on the smallest scale is of interest for the development of improved biomaterials. To date, transmission electron microscopy (TEM) has been utilized for examination of the bone-implant interface, providing details on the nanometer level. In this study we show that TEM imaging can be complemented with atom probe tomography (APT) to reveal the chemical composition of a Ti-based dental implant in a human jaw on the atomic level of resolution. Correlative microscopy ensures the accuracy of APT reconstructions and helps provide both chemical and structural information of the bone-implant interface on the smallest of length scales.

Toward a Comprehensive Mechanistic Understanding of Hydrogen Uptake in Zirconium Alloys by Combining Atom Probe Analysis With Electronic Structure Calculations

The ability of a zirconium alloy to resist corrosion relies on a compromise between two opposing strategies. Minimizing the hydrogen pickup fraction (HPUF) by invoking metallic electron conduction in the barrier oxide results in rapid parabolic oxide growth. On the other hand, slow sub-parabolic barrier oxide growth, as reflected in rate limiting electron transport, may result in a high HPUF. The objective of the present study is to offer mechanistic insights as to how low concentrations of different alloying elements become decisive for the overall corrosion behavior. Combining atomistic microanalysis with first principles modeling by means of density functional theory, the speciation and redox properties of Fe and Ni towards hydrogen evolution are firstly explored. Complementary atom probe microanalysis at the metal–oxide interface provides evidence for Fe and Ni segregation to grain boundaries in Zircaloy-2 that propagates into the ZrO2 scale. Descriptors for how alloying elements in ZrO2 control electron transport as well as catalytic electron-proton recombination in grain boundaries to form H2 are determined by means of theory. The findings are generalized by further atomistic modeling, and are thus put in the context of early reports from autoclave experiments on HPUFs of zirconium with the alloying elements Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Nb. A shunting mechanism which combines inner and outer hydrogen evolution mechanisms is proposed. Properties of the transient zirconium sub-oxide are discussed. A plausible atomistic overall understanding emerges.

Oxidation Mechanism in Zircaloy- 2—The Effect of SPP Size Distribution

The metal/oxide interface region in Zircaloy-2 oxidized in autoclave was studied with transmission electron microscopy (TEM) and atom probe tomography. In addition to waviness on the micrometer scale the metal/oxide interface was found to have irregularities on a finer scale, and metal islands were found especially at metal hills (delayed parts of the oxidation front). The thickness of the sub-oxide layer varies considerably along the interface in the same sample, from 100 to virtually 0 nm. The sub-oxide composition may vary on a very fine scale (down to 5nm), and it can sometimes be a mixture of sub-oxides with different oxygen content. The metal matrix in contact with the sub-oxide is saturated with up to 32 at. % oxygen, and the oxygen diffusion profile in the metal is in approximate agreement with literature data for pure Zr. However, the diffusion length appears to be somewhat larger at interface metal hills than under valleys, probably for both geometrical and stress state reasons. Hydride precipitates, hardly visible in conventional TEM, give a good image contrast when employing high angle annular dark field imaging. A model for the oxidation process is presented, where the creep deformation of the metal close to the interface and the formation of lateral cracks in the oxide are of highest importance. The effect of second phase particle (SPP) size is suggested to be twofold: Small and numerous SPPs give a stronger metal and therefore higher stress in the oxide. Small SPPs also nucleate many more lateral cracks in the oxide, which gives a weaker oxide. Together this leads to formation of large cracks associated with transition in the oxidation rate at an earlier time than for a material with larger and fewer SPPs, and thereby a higher oxidation rate.