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Asphaltene deposition in petroleum refineries is known to be problematic as it reduces efficiencyand may lead to structural failure or production downtime. Though several successful approacheshave been utilized to limit deposition through the addition of dispersants and inhibitors topetroleum, these methods require constant intervention and are often expensive. In this study, wedemonstrate an innovative technique to engineer the surface chemistry of pipeline alloy steels toinhibit asphaltene deposition. Pack aluminization, a standard industrial-scale chemical vapordeposition process, is employed at a low temperature of 600 oC to aluminize API 5L X65 highstrength pipe steel substrates. The results showed deposit free steel surfaces after high-pressureand high-temperature fouling experiments. The improvement is attributed to the formation of analuminide intermetallic phase of Fe2Al5, which changes the native oxide chemistry to favoralumina over hematite. The continuous passivating oxide scale, acting as a protective barrier, mitigates asphaltene deposition and sulfidic corrosion. Since this process is based on alloying thesurface of the steel and is not a coating, it is not prone to delamination, and it can be reformedwhen damaged within the aluminized region. The combination of low-cost processing andimproved anti-fouling characteristics makes surface chemistry modification of steel a promisingpreventative approach against asphaltene deposition.

Fouling of processing units because of asphaltene deposition is a common phenomenon that interrupts the operation of oil refineries. In this study, the deposition behavior of a model archipelago asphaltene was investigated in the temperature range of 150 oC to 350 oC. For a fixed surface chemistry, the differences in deposit chemistry with fouling temperature is a function of the thermochemical properties of the model asphaltene. Under static high pressure and high temperature fouling conditions, both surface roughness and chemistry play an important role in asphaltene deposition. Rough surfaces are shown to develop larger deposits because of less restrictive physical barriers to inhibit deposit growth. Passivating the surface with an alumina chemistry significantly reduces the impact of surface roughness, as well as the total amount of deposition. This beneficial effect of using a protective alumina chemistry is attributed to its high thermal stability and low diffusivity that inhibit the uncontrolled formation of thiolate and sulfide deposits that are found on unpassivated steels. Instead, alumina modifies the surface reaction to a self-limiting chemisorption and oxidation process that produces thin sulfate deposits at the surface. With further consideration to the reactive species present in solution, the findings of this study may be extended to determine suitable surface conditions that mitigate asphaltene fouling.

Fouling of oil-exposed surfaces remains a crucial issue as a result of the continued importance of oil as the world’s primary energy source. The key perpetrators in crude oil fouling have been identified as asphaltenes, a poorly described mixture of diverse polyfunctional molecules that form part of the heaviest fractions of oil. Asphaltenes are responsible for a decrease in oil production and energy efficiency and an increase in the risk of environmental hazards. Hence, understanding and managing systems that are prone to fouling is of great value but constitutes a challenge as a result of their complexity. In an effort to reduce that complexity, a study of a synthesized foulant of archipelago structure is presented. A critical perspective on previously described solubility and aggregation mechanisms (e.g., critical nanoaggrerate concentration and critical clustering concentration) is offered because the characterized system favors a continuous distribution of n-mers instead. A battery of experimental and modeling techniques have been employed to link the bulk and interfacial behavior of a representative foulant monomer to effective fouling mitigation strategies. This systematic approach defines a new multiscale methodology in the investigation of fouling systems.

A generic approach to the regiospecific synthesis of halogenated polycyclic aromatics is made possible by the one- or two-directional benzannulation reactions of readily available (ortho-allylaryl)trichloroacetates (the “BHQ” reaction). Palladium-catalysed cross-coupling reactions of the so-formed haloaromatics enable the synthesis of functionalised polycyclic aromatic hydrocarbons (PAHs) with surgical precision. Overall, this new methodology enables the facile mining of chemical space in search of new electronic functional materials.

In five straight-stemmed, proximally porous-coated femoral components that were retrieved at revision arthroplasty from patients who had radiographic and clinical evidence of loosening, there was growth of bone into the porous coating. The components had been inserted during a primary arthroplasty in one woman and four men. The patients ranged in age from thirty-seven to sixty-seven years. Three patients were heavy, and all five were active. All patients had had an excellent early result from the initial arthroplasty; at the one-year follow-up, the mean Harris hip score had been 91 points. Pain in the hip developed in all of the patients, between one and three years after the index procedure. Initial radiographs had revealed excellent position and fixation of the prosthetic components, but the components then subsided between one and three and one-half years after the index procedure. All of the femoral components were found to be grossly loose at the revision operation. Nevertheless, all of the prosthetic components demonstrated growth of bone into 4 to 44 per cent (mean, 24 per cent) of the pore spaces available for ingrowth. Woven bone and fracture callus were found in the curettings from the proximal part of the femur. The findings in these five patients suggest that late failure of uncemented porous-surfaced femoral components can occur despite the presence of extensive ingrowth of bone. These failures may be the result of fatigue fractures of the trabeculae of the osseous ingrowth into the porous surfaces. Caution is warranted in the liberal use of these prosthetic components in heavy, active patients.

We studied 16 femora retrieved at post-mortem from symptomless patients who had a satisfactory cemented total hip arthroplasty from two weeks to 17 years earlier, with the aim of delineating the initial mechanisms involved in loosening. Only one specimen showed radiographic evidence of loosening; the other 15 were stable to mechanical testing at 17.0 Nm of torque. In all 16 specimens, the cement-bone interface was intact with little fibrous tissue formation. By contrast, separation at the cement-prosthesis interface and fractures in the cement mantle were frequent. The most common early feature was debonding of the cement from the metal, seen at the proximal and distal ends of the prosthesis. Specimens which had been in place for longer also showed circumferential fractures in the cement, near the cement-metal interface, and radial fractures extending from this interface into the cement and sometimes to the bony interface. The most extensive cement fractures appeared to have started at or near sharp corners in the metal, or where the cement mantle was thin or incomplete. Fractures were also related to voids in the cement. The time relationship in this series suggested that long-term failure of the fixation of cemented femoral components was primarily mechanical, starting with debonding at the interface between the cement and the prosthesis, and continuing as slowly developing fractures in the cement mantle.

Thirteen femora that were obtained at autopsy from patients in whom a cemented total hip replacement had been implanted from forty months to 17.5 years earlier were evaluated radiographically and morphologically. All of the patients had been functioning well, and only one of the prostheses showed radiographic evidence of loosening. Serial sections of the proximal portion of the femur that enclosed the femoral component of the prosthesis showed that the host bone was intimately and directly apposed to the cement, and fibrous tissue intervened only rarely. The bone-remodeling processes had created a dense shell of substantial new bone around the cement-mantle that resembled a new cortex, attached to the outer cortex by new trabecular struts. Evidence of ingrowth of bone from this dense shell of bone into the undulating surface of the cement was found in many areas. In the adjacent femoral cortex, there was substantial osteoporosis and cortical thinning. The cement-bone interface was intact and excellent throughout, despite the presence of fractures within the cement-mantle and de-bonding at the cement-prosthesis interface in some specimens. The cemented femoral components were well tolerated by the skeleton over a long period of use, and fibrous tissue had rarely formed at the femoral cement-bone interface of these well fixed and clinically successful prostheses. The cement-mantle was well supported by extensive medullary bone-remodeling and formation of a dense shell of new bone. The internal bone-remodeling helped to maintain the cemented femoral components over time and did not cause loosening of the prosthesis.

Bone ingrowth into uncemented hemispherical canine acetabular components porous-coated with cobalt chrome spheres was compared to those porous-coated with titanium fiber mesh. While good bone ingrowth was noted in both types of porous coatings at 6 weeks after surgery with no difference in the histologic quality of the ingrown bone, quantitation of bone ingrowth showed that significantly more bone grew into titanium fiber mesh porous-coated components. The mean amount of bone ingrowth measured 10.5% of the area of the porous coating with fiber mesh coatings and only 5.5% of the area of the porous coating with spherical coatings (significant difference at P < .0005). The mean area density of the ingrown bone inside the pores measured 21.5% of the pore area with fiber mesh coatings, also significantly greater than 13.4% of the pore area with sphere coatings (P < .025). The ingrown bone penetrated a mean 66% of the depth of the porous layer with fiber mesh coatings compared to 32% of the depth of the porous layer with spherical coating (significant difference at P < .0005). The mean extent of the periphery of the porous layer with bone ingrowth was 88% for the mesh coatings and 55% for the spherical coatings (also a significant difference at P < .01).

Uncemented straight-stemmed proximally porous-coated femoral components were press fitted into the femoral canals of seven dogs using a rasp 0.5 mm smaller than the components (press-fit group). In seven other dogs the components were fit precisely into the femoral canals using a rasp that was the same size as the components (control group). Using this technique, all of the dogs in the press-fit group developed longitudinal fractures in the femoral cortex, while none of the dogs in the control group developed fractures. None of the fractures were recognized at operation. Two of the dogs in the press-fit group displaced the fractures at 1 week and were sacrificed. The other five dogs were bearing weight on their limbs and completed the 3-week experimental period. Follow-up radiographs of these femurs showed marked periosteal new bone formation, but did not reveal any fractures. Serial sections of these femurs showed longitudinal healing fractures in the anterior cortex. The fractures had an adverse effect on the bone ingrowth into the porous surface of the press-fit group compared to the control group without fractures, and the porous surface adjacent to the fractures was ingrown with fibrous tissue. The amount of bone ingrowth expressed as a percentage of the porous coating area measured, on average, only 3.9% in the press-fit group at 3 weeks compared to 5.6% in the control group--a statistically significant difference at P < .025. This experience in the dog illustrates the inherent risk of driving a larger femoral component into a smaller cavity prepared in the femur.(ABSTRACT TRUNCATED AT 250 WORDS)

Six porous-coated, uncemented femoral components were revised at a mean of 34.5 months for persistent thigh pain. At operation the stems were rigidly stable, difficult to extract, and showed good bony ingrowth. The four men and two women, with an average age of 59 years, all had thigh pain starting within the first year, progressive over time and unresponsive to conservative measures. These cases show that rigid fixation with good bony ingrowth does not guarantee the clinical success of a porous-coated uncemented femoral stem.

In five straight-stemmed, proximally porous-coated femoral components that were retrieved at revision arthroplasty from patients who had radiographic and clinical evidence of loosening, there was growth of bone into the porous coating. The components had been inserted during a primary arthroplasty in one woman and four men. The patients ranged in age from thirty-seven to sixty-seven years. Three patients were heavy, and all five were active. All patients had had an excellent early result from the initial arthroplasty; at the one-year follow-up, the mean Harris hip score had been 91 points. Pain in the hip developed in all of the patients, between one and three years after the index procedure. Initial radiographs had revealed excellent position and fixation of the prosthetic components, but the components then subsided between one and three and one-half years after the index procedure. All of the femoral components were found to be grossly loose at the revision operation. Nevertheless, all of the prosthetic components demonstrated growth of bone into 4 to 44 per cent (mean, 24 per cent) of the pore spaces available for ingrowth. Woven bone and fracture callus were found in the curettings from the proximal part of the femur. The findings in these five patients suggest that late failure of uncemented porous-surfaced femoral components can occur despite the presence of extensive ingrowth of bone. These failures may be the result of fatigue fractures of the trabeculae of the osseous ingrowth into the porous surfaces. Caution is warranted in the liberal use of these prosthetic components in heavy, active patients.

Thirteen femora that were obtained at autopsy from patients in whom a cemented total hip replacement had been implanted from forty months to 17.5 years earlier were evaluated radiographically and morphologically. All of the patients had been functioning well, and only one of the prostheses showed radiographic evidence of loosening. Serial sections of the proximal portion of the femur that enclosed the femoral component of the prosthesis showed that the host bone was intimately and directly apposed to the cement, and fibrous tissue intervened only rarely. The bone-remodeling processes had created a dense shell of substantial new bone around the cement-mantle that resembled a new cortex, attached to the outer cortex by new trabecular struts. Evidence of ingrowth of bone from this dense shell of bone into the undulating surface of the cement was found in many areas. In the adjacent femoral cortex, there was substantial osteoporosis and cortical thinning. The cement-bone interface was intact and excellent throughout, despite the presence of fractures within the cement-mantle and de-bonding at the cement-prosthesis interface in some specimens. The cemented femoral components were well tolerated by the skeleton over a long period of use, and fibrous tissue had rarely formed at the femoral cement-bone interface of these well fixed and clinically successful prostheses. The cement-mantle was well supported by extensive medullary bone-remodeling and formation of a dense shell of new bone. The internal bone-remodeling helped to maintain the cemented femoral components over time and did not cause loosening of the prosthesis.

Late aseptic loosening of cemented acetabular components is governed by the progressive, three-dimensional resorption of the bone immediately adjacent to the cement mantle. This process begins circumferentially at the intraarticular margin and progresses toward the dome of the implant. Evidence of bone resorption at the cement-bone interface was present even in the most well-fixed implants before the appearance of lucent lines on standard roentgenographic views. The mechanical stability of the implant was determined by the three-dimensional extent of bone resorption and membrane formation at the cement-bone interface. The leading edge of the membrane is a transition zone from regions of membrane interposition between the cement and the bone to regions of intimate cement-bone contact. Histologic analysis revealed that progressive bone resorption is fueled by small particles of high density polyethylene (HDP) migrating along the cement-bone interface and bone resorption occurs as a result of the macrophage inflammatory response to the particulate HDP. Evidence in support of a mechanical basis for failure of fixation was lacking. The mechanism of late aseptic loosening of a cemented acetabular component is therefore biologic in nature, not mechanical. This is exactly opposite to the mechanism of loosening on the femoral side of a cemented total hip replacement, which is mechanical in nature.

Bone ingrowth into titanium fiber mesh porous-surfaced canine total hip replacement prostheses was evaluated and quantified using a computer assisted image analysis system attached to a scanning electron microscope equipped with a back scattered electron detector. Excellent contrast between the bone, the porous metal and the soft tissues resulted in the backscatter mode, allowing easy differentiation of these components in real time by the image analysis based on gray scales. By three weeks the mean (+/- standard deviation) amount of bone ingrowth expressed as a percentage of porous layer measured 7.2% (+/- 1.5%) for the acetabular components, and 3.9% (+/- 1.7%) for the femoral components. At six weeks the amount of bone ingrowth increased to 10.5% (+/- 1.3%) for the acetabular components and 8.5% (+/- 1.4%) for the femoral components. Cementless prosthetic fixation using porous surfaced prostheses holds great promise in joint replacement surgery, and the ability to quantitate the amount of bone ingrowth will permit the evaluation of the efficacy of various techniques to improve bone ingrowth.

This paper presents methods and data for applying statistical concepts to the design and analysis of structures. It is based on work done by The Martin Company in connection with the Titan II missile program. Statistical description of loads and strengths is discussed in terms of the normal probability theory. The relations between reliability and the statistical parameters of strength and load are given in the form of a design chart. A practical method for deriving the normal standard deviation from limited test data is explained. A chart is provided for easy graphical analysis. Engineering values of coefficient of variation for typical structures strengths are included. Finally, a practical example is given of the benefits to be derived from reliability analysis.

IL-12 is a potent inducer of NK and cytolytic T cell activity, IFN-gamma production, and T cell proliferation, and is necessary for differentiation of naive T cells to the Th1 subset. We have previously shown that IL-12 promotes a primary Th1 response and suppresses a primary Th2 response in lymph nodes of mice primed with a model hapten-protein conjugate, 2,4,6-trinitrophenyl (TNP)-keyhole limpet hemocyanin (KLH). We have now extended these studies to determine the Th phenotype of the recall response following immunization with soluble Ag and IL-12. For these experiments, mice were primed with TNP-KLH with or without treatment with IL-12, allowed to progress beyond the primary immune response, and challenged by i.p. injection of TNP-KLH. The phenotype of the recall response was monitored by measuring ex vivo production of IFN-gamma and IL-4 in Ag-stimulated lymph node and spleen cell cultures. Titer and isotype of TNP-specific serum Abs were also evaluated. Mice primed with Ag+IL-12 developed a Th1 recall response, as detected by KLH-specific IFN-gamma production from cultured spleen cells and the presence of TNP-specific IgG2a Ab in serum. However, they also developed an Ag-specific Th2 recall response, as characterized by Ag-induced IL-4 production from spleen cells and the presence of high titers of anti-TNP IgG1 in the serum. Studies of the cytokine profile during the primary response revealed that IL-12 induced in spleen cells the capacity to express both IL-4 and IFN-gamma. CD4+ T cells are necessary for production of IL-4 in the spleens of IL-12-treated mice, and most likely account for the Th2 recall response detected in mice primed with Ag+IL-12. These results indicate that the Th1 phenotype induced by immunization with IL-12 and Ag is maintained so that a Th1 recall response is expressed upon subsequent challenge with Ag. However, immunization with IL-12 also supports the development of a Th2 recall response, indicating that the Th1-inducing effect of IL-12 in vivo is not accompanied by a long lasting suppression of Th2 development.