Structural modifications induced by compressive plastic deformation in single-step and sequentially irradiated UHMWPE for hip joint components

Structural modifications were studied at the molecular scale in two highly crosslinked UHMWPE materials for hip-joint acetabular components, as induced upon application of (uniaxial) compressive strain to the as-manufactured microstructures. The two materials, quite different in their starting resins and belonging to different manufacturing generations, were a single-step irradiated and a sequentially irradiated polyethylene. The latter material represents the most recently launched gamma-ray-irradiated polyethylene material in the global hip implant market. Confocal/polarized Raman spectroscopy was systematically applied to characterize the initial microstructures and the microstructural response of the materials to plastic deformation. Crystallinity fractions and preferential orientation of molecular chains have been followed up during in vitro deformation tests on unused cups and correlated to plastic strain magnitude and to the recovery capacity of the material. Moreover, analyses of the in vim deformation behavior of two short-term retrieved hip cups are also presented. Trends of preferential orientation of molecular chains as a function of residual strain were similar for both materials, but distinctly different in their extents. The sequentially irradiated material was more resistant to plastic deformation and, for the same magnitude of residual plastic strain, possessed a higher capacity of recovery as compared to the single-step irradiated one. (C) 2013 Elsevier Ltd. All rights reserved

Raman tensor analysis of ultra-high molecular weight polyethylene and its application to study retrieved hip joint components

The angular dependences of the polarized Raman intensity of A(g), B-1g, B-2g, and B-3g modes have been preliminary investigated on a model fiber sample of ultra-high molecular weight polyethylene (UHMWPE) in order to retrieve the Raman tensor elements, i.e. the intrinsic parameters governing the vibrational behavior of the orthorhombic structure of polyethylene. Based on this Raman analysis, a method is proposed for determining unknown crystallographic orientation patterns in UHMWPE biomedical components concurrently with the orientation distribution functions for orthorhombic lamellae. An application of the method is shown, in which we quantitatively examined the molecular orientation patterns developed on the surface of four in vivo exposed UHMWPE acetabular cups vs. an unused cup. Interesting findings were: (i) a clear bimodal distribution of orientation angles was observed on worn surfaces; and (ii) a definite and systematic increase in both molecular orientation and crystallinity in main wear zones vs. non-wear zones was found in all retrieved acetabular cups. The present crystallographic analysis is an extension of our previous Raman studies of UHMWPE acetabular cups related to assessments of oxidation and residual strain and suggests a viable path to track back wear-history information from the surface of UHMWPE, thus unfolding the in vivo kinematics of the bearing surfaces in hip joints on the microscopic scale. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved

Structural profile of ultra-high molecular weight polyethylene in acetabular cups worn on hip simulators characterized by confocal Raman spectroscopy

We applied a Raman confocal spectroscopic technique to quantitatively assess the structural features of two kinds of acetabular cups made of ultra-high molecular weight polyethylene. We wanted to know whether polyethylene cups belonging to different generations, and thus manufactured by different procedures, possess different molecular structures and how those differences affected their wear resistance. Emphasis was placed on oxidation profiles developed along the cross-sectional depth of the cups in the main wear zone developed during testing in a hip simulator. The micrometric lateral resolution of the laser beam, focused at surface or sub-surface sectional planes, enabled the visualization of highly resolved microstructural property profiles, including crystalline and amorphous phase fractions. Oxidation profiles retrieved from polyethylene cups belonging to different generations greatly differed after wear testing. The highly cross-linked polyethylene showed a lower degree of crystallinity and oxidation at an appreciably slower rate as compared to that belonging to an earlier generation. (C) 2011 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 29:893-899, 201

Polarized Raman analysis of the molecular rearrangement and residual strain on the surface of retrieved polyethylene tibial plates

The response to applied strain of EtO-sterilized and gamma-irradiated polyethylene materials belonging to tibial inserts has been studied by polarized Raman spectroscopy. Initial calibrations on as-received samples from three different makers were employed to clarify the rearrangement of molecular chains under strain, expressed in terms of Euler angular displacements in space and orientation distribution functions. This body of information was then applied to a quantitative analysis of four tibial inserts (from the same three makers of the unused samples) retrieved after in vivo exposures ranging between 7 months and 5 years 8 months. The main results of the Raman analysis can be summarized as follows: (i) gamma-irradiated samples experienced lower texturing on the molecular scale compared to EtO-sterilized samples, likely due to a higher strain recovery capability; and (ii) independent of sterilization method, the amount of plastic strain was mainly developed early after in vivo implantation, whereby out-of-plane molecules rotated under load onto planes parallel to the sample surface until saturation of angular displacements was reached. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved

Innovative tribometer for in situ spectroscopic analyses of wear mechanisms and phase transformation in ceramic femoral heads

The literature on tribological assessments of artificial hip joints usually focuses on correlations between joint composition, size, and specific wear rates, but conspicuously ignores the physical aspects behind the occurrence of degradation mechanisms of friction and wear. Surface degradation in artificial joints occurs because of increases in temperature and local exacerbation of contact stresses inside the moving contact as a consequence of physical and chemical modifications of the sliding surfaces. This article reports about the development of a new pin-on-ball spectroscopy-assisted tribometer device that enables investigating also physical rather than merely engineering aspects of wear processes using in situ Raman and fluorescence techniques. This innovative tribometer is designed to bring about, in addition to conventional tribological parameters, also information of temperature, stress and phase transformations in the femoral heads as received from the manufacturer Raman and fluorescence spectra at the point of sliding contact are recorded durilng reciprocating hard-on-hard dry-sliding tests. Preliminary results were collected on two different commercially available ceramic-on-ceramic hip joint bearing couples, made of monolithic alumina and alumina-zirconia composites. Although the composite couple showed direct evidence of tetragonal-to-monoclinic phase transformation, which enhanced the coefficient of friction, the specific wear rate was significantly lower than that of the monolithic one (i.e., by a factor 2.63 and 4.48 on the pin and head side, respectively). In situ collected data compared to ex situ analyses elucidated the surface degradation processes and clarified the origin for the higher wear resistance of the composite as compared to the monolithic couple. (C) 2013 Elsevier Ltd. All rights reserved

In-depth oxidation and strain profiles in UHMWPE acetabular cups non-destructively studied by confocal Raman microprobe spectroscopy

Raman spectroscopy is used for the characterization of the two main mechanisms responsible for the degradation of acetabular cups in hip joints: creep deformation and oxidation. The term creep refers to the permanent deformation that occurs under the effect of body weight and does not completely recover after load release. This mechanism involves no mass loss from the sample, but packing and adjustment of the polyethylene molecules in their reciprocal positions under pressure. Conversely, oxidation triggers wear, which is accompanied by irreversible mass loss from the material: surface molecules of the polyethylene body oxidize, delaminate and are progressively peeled off, involving volumetric changes and resulting in debris formation. Both degradation mechanisms negatively interact and converge toward cup loosening, which requires revision surgery. In this paper, we show that confocal Raman spectroscopy can be used to separate the contributions to the dimensional change observed in acetabular cups arising from creep and from wear. Raman measurements are completely non-destructive and contactless, and can guide surgeons and materials technologists to optimize surface treatments and molecular structure of polyethylene cups, thus maximizing their in vivo lifetime. (C) Koninklijke Brill NV, Leiden, 200

Raman spectroscopic study of remelting and annealing-induced effects on microstructure and compressive deformation behavior of highly crosslinked UHMWPE for total hip arthroplasty

Three-dimensional crystallographic morphologies were studied by means of confocal/polarized Raman spectroscopy as developed upon manufacturing in three different types of first and second generation highly crosslinked UHMWPE (HXLPE) acetabular liners. The impact of such microstructural characteristics on the deformation behavior of the liners was also evaluated and discussed from the viewpoint of molecular chain mobility. All the investigated liners showed similar microstructural transitions within the first 35 mu pm below their surfaces in terms of crystallinity, molecular orientation, and crystalline anisotropy. Interestingly, different postirradiation heat treatments (remelting or annealing in single step or in sequential steps) led to clear differences in the subsurface microstructure among the three liners. Remelted liner possessed both lower bulk crystallinity and degree of molecular orientation as compared to the annealed liners. Sequentially, irradiated/annealed liner showed the highest degree of crystallinity and orientation among the studied liners. The peculiar microstructure of this latter liner exhibited the highest restoring (shape-recovery) force against the applied uniaxial strain. Accordingly, the present study suggests that the sequential irradiation and annealing offers an efficient way to obtain microstructure quite suitable for attaining high creep resistance. However, all the investigated liners exhibited the significantly low values of surface anisotropy, which could be equally efficient in minimizing strain-softening-assisted wear phenomena. (C) 2014 Wiley Periodicals, Inc

In situ measurements of local temperature and contact stress magnitude during wear of ceramic-on-ceramic hip joints

Fluorescence microprobe spectroscopy was applied to in situ assessments of contact stress and local temperature at the contact point of dry-sliding couples during wear tests of two commercially available ceramic-on-ceramic femoral heads. The investigated ceramic hip implants consisted of either monolithic Al2O3 or Al2O3/ZrO2 composite. A specially designed pin-on-ball tribometer was employed, which enabled directly testing the femoral head components as received from the maker without further manipulation. The strong fluorescence emission from Cr3+ impurities contained in Al2O3 served as a responsive sensor for both temperature and stress. Analytical corrections for the averaging effects arising from the finite size of the laser probe were made according to a probe response formalism in which geometrical conditions of the sliding couple were incorporated as boundary conditions. The sample-probe interaction at the contact point was then experimentally calibrated by obtaining probe response functions for the two materials investigated. Based on such theoretical and experimental procedures, deconvolutive computational routines could be set up and the true variations of local temperature and stress at the contact point of the bearing surfaces retrieved from the observed time-dependent broadening and shift of a selected spectral band, respectively. The main result of the in situ investigation was that the monolithic sliding couple showed both significantly lower temperature and lower magnitude of compressive stress at the contact point as compared to the composite one, although the composite couple wore at a significantly lower specific wear rate than the monolithic one. (C) 2013 Elsevier Ltd. All rights reserved

Failure analysis of sandwich-type ceramic-on-ceramic hip joints: A spectroscopic investigation into the role of the polyethylene shell component

The mechanisms leading to systematic failure in modular acetabular components with a sandwich insertion (alumina/polyethylene/titanium) have been reconsidered in light of the newly collected Raman spectroscopic results. Raman assessments were conducted on the polyethylene shells, which belonged to a series of six failed sandwich implants with in vivo lifetimes ranging between 2 and 9 yr. With only one exception, all implants commonly showed dislodgment of the polyethylene shell during radiographic analyses prior to revision surgery. The polyethylene shell slipped out of the backing titanium shell, while always remaining integer to the ceramic liner. Four implants fractured at the ceramic liners, but their fractures occurred according to distinctly different patterns, which could be rationalized and classified. The insertion of the polyethylene layer, originally conceived to reduce the rigidity of the ceramic-on-ceramic bearing and to prevent impingement between the ceramic liner rim and the femoral neck, played a role in implant failure with its initial (asymmetric) thickness reduction due to creep deformation (eventually followed by cup rotation and backside wear). The results of the present spectroscopic investigation suggest that a simplistic failure classification of the sandwich-type implant as a "ceramic fracture failure" could be misleading and might represent a confounding factor in judging about the reliability of modern ceramic implants. (C) 2013 Elsevier Ltd. All rights reserved

Non-destructively differentiating the roles of creep, wear and oxidation in long-term in vivo exposed polyethylene cups

Wear of polyethylene acetabular cups in patients of total hip arthroplasty is routinely deduced from the penetration of the femoral head into the acetabular liner as observed in the radiographs. However, the linear penetration thus measured represents the cumulative contribution of two components, one due to wear, and the other due to creep or irreversible deformation of the polyethylene structure. The erroneous attribution to wear of the entire penetration displacement of the head in the cup might lead to misinterpretation of the actual performance of acetabular cups. The aim of this study was to quantify the head displacement components due to wear and to creep, as they occur in vivo in acetabular cups, and to relate them to the oxidation state of the material by means of advanced Raman spectroscopy procedures. Throughout the investigation, we compared the behaviors on the molecular scale of acetabular cups subjected to different sterilization methods (i.e., gamma-irradiation and ethylene oxide treatment). (C) Koninklijke Brill NV, Leiden, 201