Improving fretting corrosion resistance of CoCrMo alloy with TiSiN and ZrN coatings for orthopedic applications.

Total hip replacement is the most effective treatment for late stage osteoarthritis. However, adverse local tissue reactions (ALTRs) have been observed in patients with modular total hip implants. Although the detailed mechanisms of ALTRs are still unknown, fretting corrosion and the associated metal ion release from the CoCrMo femoral head at the modular junction has been reported to be a major factor. The purpose of this study is to increase the fretting corrosion resistance of the CoCrMo alloy and the associated metal ion release by applying hard coatings to the surface. Cathodic arc evaporation technique (arc-PVD) was used to deposit TiSiN and ZrN hard coatings on CoCrMo substrates. The morphology, chemical composition, crystal structures and residual stress of the coatings were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffractometry. Hardness, elastic modulus, and adhesion of the coatings were measured by nano-indentation, nano-scratch test, and the Rockwell C test. Fretting corrosion resistance tests of coated and uncoated CoCrMo discs against Ti6Al4V spheres were conducted on a four-station fretting testing machine in simulated body fluid at 1Hz for 1 million cycles. Post-fretting samples were analyzed for morphological changes, volume loss and metal ion release. Our analyses showed better surface finish and lower residual stress for ZrN coating, but higher hardness and better scratch resistance for TiSiN coating. Fretting results demonstrated substantial improvement in fretting corrosion resistance of CoCrMo with both coatings. ZrN and TiSiN decreased fretting volume loss by more than 10 times and 1000 times, respectively. Both coatings showed close to 90% decrease of Co ion release during fretting corrosion tests. Our results suggest that hard coating deposition on CoCrMo alloy can significantly improve its fretting corrosion resistance and could thus potentially alleviate ALTRs in metal hip implants.

Differential response of human blood leukocytes to brushite, monetite, and calcium polyphosphate biomaterials.

Calcium phosphate-based biomaterials are extensively used for bone replacement and regeneration in orthopedic, dental, and maxillofacial surgical applications. The injury induced by surgical implantation of bone replacement graft materials initiates a cascade of host responses, starting with blood-biomaterial contact, protein adsorption on the material surface, blood coagulation, and leukocyte responses. During the initial acute inflammatory response, polymorphonuclear neutrophils (PMNs) and monocytes, abundant circulating leukocytes of the myeloid lineage, are recruited to the site of inflammation. In addition to responding to pathogenic challenges, these cells respond to particulate substances within the body including crystals of monosodium urate (MSU). Host responses toward grafts impact short- and long-term success in tissue engineering and regenerative applications. Although multinucleated osteoclasts, formed by monocyte/macrophage fusion, are generally thought to be responsible for resorption of implant biomaterials, the ability of different biomaterials to trigger PMNs, which are invariably present at the early stages after implant surgery, and are abundant in the oral cavity, has never been tested. In this article, we present analysis of the response of human blood-derived PMNs and monocytes toward brushite, monetite, and calcium polyphosphate (CPP) biomaterial substrates and compare this to the response to MSU crystals, the latter serving as a positive control. Employing multicolor flow cytometry to look at PMN and monocyte cell surface markers of activation to gauge the response to different biomaterials, we found that both types of myeloid cells are highly activated after exposure to brushite, monetite, and MSU but not CPP. © 2019 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 108B:253-262, 2020.

Calcium polyphosphate particulates for bone void filler applications.

This study investigates the characteristics of porous calcium polyphosphate particulates (CPPp) formed using two different processing treatments as bone void fillers in non- or minimally load-bearing sites. The two calcium polyphosphate particulate variants (grades) were formed using different annealing conditions during particulate preparation to yield either more slowly degrading calcium polyphosphate particulates (SD-CPPp) or faster degrading particulates (FD-CPPp) as suggested by a previous degradation study conducted in vitro (Hu et al., Submitted for publication 2016). The two CPPp grades were compared as bone void fillers in vivo by implanting particulates in defects created in rabbit femoral condyle sites (critical size defects). The SD-CPPp and FD-CPPp were implanted for 4- and 16-week periods. The in vivo study indicated a significant difference in amount of new bone formed in the prepared sites with SD-CPPp resulting in more new bone formation compared with FD-CPPp. The lower bone formation characteristic of the FD-CPPp was attributed to its faster degradation rate and resulting higher local concentration of released polyphosphate degradation products. The study results indicate the importance of processing conditions on preparing calcium polyphosphate particulates for potential use as bone void fillers in nonload-bearing sites. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 874-884, 2017.

Phase transformations during processing and in vitro degradation of porous calcium polyphosphates.

A 2-Step sinter/anneal treatment has been reported previously for forming porous CPP as biodegradable bone substitutes [9]. During the 2-Step annealing treatment, the heat treatment used strongly affected the rate of CPP degradation in vitro. In the present study, x-ray diffraction and (31)P solid state nuclear magnetic resonance were used to determine the phases that formed using different heat treating processes. The effect of in vitro degradation (in PBS at 37 °C, pH 7.1 or 4.5) was also studied. During CPP preparation, ß-CPP and γ-CPP were identified in powders formed from a calcium monobasic monohydrate precursor after an initial calcining treatment (10 h at 500 °C). Melting of this CPP powder (at 1100 °C), quenching and grinding formed amorphous CPP powders. Annealing powders at 585 °C (Step-1) resulted in rapid sintering to form amorphous porous CPP. Continued annealing to 650 °C resulted in crystallization to form a multi-phase structure of ß-CPP primarily plus lesser amounts of α-CPP, calcium ultra-phosphates and retained amorphous CPP. Annealing above 720 °C and up to 950 °C transformed this to ß-CPP phase. In vitro degradation of the 585 °C (Step-1 only) and 650 °C Step-2 annealed multi-phase samples occurred significantly faster than the ß-CPP samples formed by Step-2 annealing at or above 720 °C. This faster degradation was attributable to preferential degradation of thermodynamically less stable phases that formed in samples annealed at 650 °C (i.e. α-phase, ultra-phosphate and amorphous CPP). Degradation in lower pH solutions significantly increased degradation rates of the 585 and 650 °C annealed samples but had no significant effect on the ß-CPP samples.

Porous calcium polyphosphate bone substitutes: additive manufacturing versus conventional gravity sinter processing-effect on structure and mechanical properties.

Porous calcium polyphosphate (CPP) structures proposed as bone-substitute implants and made by sintering CPP powders to form bending test samples of approximately 35 vol % porosity were machined from preformed blocks made either by additive manufacturing (AM) or conventional gravity sintering (CS) methods and the structure and mechanical characteristics of samples so made were compared. AM-made samples displayed higher bending strengths (≈1.2-1.4 times greater than CS-made samples), whereas elastic constant (i.e., effective elastic modulus of the porous structures) that is determined by material elastic modulus and structural geometry of the samples was ≈1.9-2.3 times greater for AM-made samples. X-ray diffraction analysis showed that samples made by either method displayed the same crystal structure forming ß-CPP after sinter annealing. The material elastic modulus, E, determined using nanoindentation tests also showed the same value for both sample types (i.e., E ≈ 64 GPa). Examination of the porous structures indicated that significantly larger sinter necks resulted in the AM-made samples which presumably resulted in the higher mechanical properties. The development of mechanical properties was attributed to the different sinter anneal procedures required to make 35 vol % porous samples by the two methods. A primary objective of the present study, in addition to reporting on bending strength and sample stiffness (elastic constant) characteristics, was to determine why the two processes resulted in the observed mechanical property differences for samples of equivalent volume percentage of porosity. An understanding of the fundamental reason(s) for the observed effect is considered important for developing improved processes for preparation of porous CPP implants as bone substitutes for use in high load-bearing skeletal sites.

Solid freeform fabrication of porous calcium polyphosphate structures for bone substitute applications: in vivo studies.

Porous calcium polyphosphate (CPP) structures with 30 volume percent porosity and made by solid freeform fabrication (SFF) were implanted in rabbit femoral condyle sites for 6-wk periods. Two forms of SFF implants with different stacked layer orientation were made in view of prior studies reporting on anisotropic/orthotropic mechanical properties of structures so formed. In addition, porous CPP implants of equal volume percent porosity made by conventional sintering and machining methods were prepared. Bone ingrowth and in vivo degradation of the three different implant types were compared using back-scattered scanning electron microscopy (BS-SEM) of implant samples and quantitative analysis of the images. The results indicated bone ingrowth with all samples resulting in 30-40% fill of available porosity by bone within the 6-wk period. In the 6-wk in vivo period, approximately 7-9% loss of CPP by degradation had occurred.

Porous calcium polyphosphate as load-bearing bone substitutes: in vivo study.

Porous calcium polyphosphate (CPP) is being investigated for fabrication of novel biodegradable bone substitutes. In this study, porous CPP implants formed by conventional CPP powder packing and using a two-step sinter/anneal process was used to form 20 and 30 vol % porous samples displaying relatively high strength. These were implanted in rabbit femoral condyle sites to study their ability for secure fixation in prepared sites through bone ingrowth. Porous implants of 20 and 30 vol % porosity and displaying compressive strengths ~80 and 35 MPa, respectively, were used. Bone ingrowth sufficient to allow secure implant fixation was observed by 6 weeks (~19% bone ingrowth per available pore space for the 30 vol % and 13% for the 20 vol % porous implants). The results of the in vivo study suggest the potential usefulness of porous CPP as biodegradable bone substitutes/augments in high load-bearing skeletal regions.

Mechanical characteristics of solid-freeform-fabricated porous calcium polyphosphate structures with oriented stacked layers.

This study addresses the mechanical properties of calcium polyphosphate (CPP) structures formed by stacked layers using a powder-based solid freeform fabrication (SFF) technique. The mechanical properties of the 35% porous structures were characterized by uniaxial compression testing for compressive strength determination and diametral compression testing to determine tensile strength. Fracture cleavage surfaces were analyzed using scanning electron microscopy. The effects of the fabrication process on the microarchitecture of the CPP samples were also investigated. Results suggest that the orientation of the stacked layers has a substantial influence on the mechanical behavior of the SFF-made CPP samples. The samples with layers stacked parallel to the mechanical compressive load are 48% stronger than those with the layers stacked perpendicular to the load. However, the samples with different stacking orientations are not significantly different in tensile strength. The observed anisotropic mechanical properties were analyzed based on the physical microstructural properties of the CPP structures.

Enhanced gap filling and osteoconduction associated with alendronate-calcium phosphate-coated porous tantalum.

BACKGROUND: Porous tantalum has been shown to be effective in achieving bone ingrowth. However, in some circumstances, bone quality or quantity may be insufficient to allow adequate bone ingrowth. We hypothesized that local delivery of alendronate from porous tantalum would enhance the ability of the tantalum to achieve bone ingrowth when there is a gap between the implant and bone. We evaluated the effect of alendronate-coated porous tantalum on new bone formation in an animal model incorporating a gap between the implant and bone. METHODS: A cylindrical porous tantalum implant was implanted in the distal part of each femur in eighteen rabbits (a total of thirty-six implants) and left in situ for four weeks. Three types of porous tantalum implants were inserted: those with no coating (the control group), those with microporous calcium phosphate coating, and those coated with microporous calcium phosphate and alendronate. Subcutaneous fluorescent labeling was used to track new bone formation. Bone formation was analyzed with backscattered electron microscopy and fluorescent microscopy of undecalcified samples. RESULTS: The relative increases in the mean volume of gap filling, bone ingrowth, and total bone formation in the group treated with the porous tantalum implants coated with calcium phosphate and alendronate were 143% (p < 0.001), 259% (p < 0.001), and 193% (p < 0.001), respectively, compared with the values in the control group treated with the uncoated porous tantalum implants. The percentage of the length of the implant that was in contact with new bone in the group treated with the calcium phosphate and alendronate coating was increased by an average of 804% compared with the percentage in the group treated with the uncoated implants. CONCLUSIONS: The study demonstrated significantly enhanced filling of the bone-implant gap and bone ingrowth in association with the porous tantalum implants coated with calcium phosphate and alendronate.